One-pot, high-performance recycling of polymer waste using renewable polymer synthesis

ABSTRACT

Curable formulations, cured formulations, and mixtures and composites thereof are described herein, as well as methods of making and using the formulations, mixtures, and composites.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. application Ser. No.14/204,458, filed on Mar. 11, 2014, issuing as U.S. Pat. No. 9,441,084on Sep. 13, 2016, which claims priority to and benefit of U.S.Provisional Application No. 61/779,078, filed on Mar. 13, 2013, and U.S.Provisional Application No. 61/897,010, filed on Oct. 29, 2013. Thisapplication also claims priority to and benefit of U.S. ProvisionalApplication No. 62/338,857, filed on May 19, 2016. These are herebyincorporated herein by reference in their entirety.

FIELD OF THE INVENTION

This invention is in the field of monomers, oligomers, polymers,additive and composites and methods of making and using thereof. Theinvention includes solvent chemical compositions, polymericformulations, methods of synthesis, and fabrication methods of polymers.

BACKGROUND OF THE INVENTION

Synthetic materials improve human life in tremendous ways, and materialsinnovation has played a major role in shaping the evolution of moderntechnology. Unfortunately, many materials on and with which our societyis built afford tremendous environmental problems. Approximately 23% ofall fossil fuel greenhouse gas (GHG) emissions arise from materialproduction, society throws away 590 billion pounds of non-degradablepolymer waste into the environment each year, and the toxic and wastefulprocesses used to produce many materials bring dangerous chemicals intoour homes and the environment.

When manufacturers select materials to use in their products, materialperformance, processing capability and economics largely drive thematerial selection process. Additionally, while materials' environmentalimpacts are often factored into the material selection process,environmental considerations alone rarely drive material adoption.

Thus, there exists in society a materials problem, in particular, formaterials with higher performance qualities, better processingcapabilities, and more competitive economics.

Therefore, it is an object of the invention to provide novel curableformulations with higher performance qualities, better processingcapabilities, and more competitive economics.

It is a further object to provide new formulations, methods of making,manufacturing methods thereof and articles of manufacture made from suchformulations having improved performance, tunable properties,processing, cost, and environmental benefits.

SUMMARY OF THE INVENTION

Curable formulations which possess tunable chemical functionalities andphysical properties that enable the syntheses of new materials,composites, and articles of manufacture have been developed. Specificembodiments include: Curable formulations which are formed frommonomers, oligomers, and which can be cured, formed into blends orcomposites containing fillers and/or additives; Methods of making suchcurable formulations, cured formulations thereof, and compositesthereof; (3) Methods of using and manufacturing articles formed fromsuch curable formulations, cured formulations thereof, and compositesthereof; and (4) Articles of manufacture formed from such compounds,materials, composites, and compositions thereof.

In these embodiments, curable formulations of monomeric and/oroligomeric precursors are formed via chemistries that enable desirablematerial performance and tunable physical and thermomechanicalproperties to be obtained. Desirable material performance and tunablephysical and thermomechanical properties include, but are not limitedto, high toughness, optical clarity, high tensile strength, good solventresistance, good thermal resistance, tunable modulus, viscosity, tunableglass transition temperature, tunable cure time, and tunable surfaceadhesion. Composites and other compositions thereof can be formed fromthe curable formulations.

Methods for making the curable formulations, cured formulations thereof,and other composites thereof are also described herein. In someembodiments, the methods are low waste methods which generally do notrequire any or any significant purification of the formulations,composites, or of reaction products therein. The curable or curedformulations, composites, and other compositions thereof formed from theprecursors as described above and as shown in the examples generallyproceed in additive “one pot” steps.

The curable formulations also permit for their use in methods ofmanufacture, such as thin-film deposition, 3-D printing, and coating ofsubstrates. Methods that are used to manufacture materials from thecurable formulations are significantly influenced by material processingcapability, and processing capability often refers to a material'sability to be successfully and efficiently subjected to various methodsof manufacture.

DETAILED DESCRIPTION OF THE INVENTION I. Definitions

As used herein, the term “analog” refers to a chemical compound with astructure similar to that of another (reference compound) but differingfrom it in respect to a particular component, functional group, atom,etc. As used herein, the term “derivative” refers to compounds which areformed from a parent compound by chemical reaction(s). These differencesin suitable analogues and derivatives include, but are not limited to,replacement of one or more functional groups on the ring with one ormore different functional groups or reacting one or more functionalgroups on the ring to introduce one or more substituents.

“Aryl”, as used herein, refers to 5-, 6- and 7-membered aromatic,heterocyclic, fused aromatic, fused heterocyclic, biaromatic, orbiheterocyclic ring system, optionally substituted by halogens, alkyl-,alkenyl-, and alkynyl-groups. Broadly defined, “Ar”, as used herein,includes 5-, 6- and 7-membered single-ring aromatic groups that mayinclude from zero to four heteroatoms, for example, benzene, pyrrole,furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole,pyridine, pyrazine, pyridazine and pyrimidine, and the like. Those arylgroups having heteroatoms in the ring structure may also be referred toas “aryl heterocycles” or “heteroaromatics”. The aromatic ring can besubstituted at one or more ring positions with such substituents asdescribed herein, for example, halogen, azide, alkyl, aralkyl, alkenyl,alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino,amido, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether,alkylthio, sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl,aromatic or heteroaromatic moieties, —CF₃, —CN, or the like. The term“Ar” also includes polycyclic ring systems having two or more cyclicrings in which two or more carbons are common to two adjoining rings(the rings are “fused rings”) where at least one of the rings isaromatic, e.g., the other cyclic rings can be cycloalkyls,cycloalkenyls, cycloalkynyls, aryls and/or heterocycles. Examples ofheterocyclic ring include, but are not limited to, benzimidazolyl,benzofuranyl, benzothiofuranyl, benzothiophenyl, benzoxazolyl,benzoxazolinyl, benzthiazolyl, benztriazolyl, benztetrazolyl,benzisoxazolyl, benzisothiazolyl, benzimidazolinyl, carbazolyl, 4aHcarbazolyl, carbolinyl, chromanyl, chromenyl, cinnolinyl,decahydroquinolinyl, 2H,6H-1,5,2-dithiazinyl, dihydrofuro[2,3b]tetrahydrofuran, furanyl, furazanyl, imidazolidinyl, imidazolinyl,imidazolyl, 1H-indazolyl, indolenyl, indolinyl, indolizinyl, indolyl,3H-indolyl, isatinoyl, isobenzofuranyl, isochromanyl, isoindazolyl,isoindolinyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl,methylenedioxyphenyl, morpholinyl, naphthyridinyl,octahydroisoquinolinyl, oxadiazolyl, 1,2,3-oxadiazolyl,1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, oxazolidinyl,oxazolyl, oxindolyl, pyrimidinyl, phenanthridinyl, phenanthrolinyl,phenazinyl, phenothiazinyl, phenoxathinyl, phenoxazinyl, phthalazinyl,piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, piperonyl,pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl,pyrazolyl, pyridazinyl, pyridooxazole, pyridoimidazole, pyridothiazole,pyridinyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolinyl, 2H-pyrrolyl,pyrrolyl, quinazolinyl, quinolinyl, 4H-quinolizinyl, quinoxalinyl,quinuclidinyl, tetrahydrofuranyl, tetrahydroisoquinolinyl,tetrahydroquinolinyl, tetrazolyl, 6H-1,2,5-thiadiazinyl,1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl,1,3,4-thiadiazolyl, thianthrenyl, thiazolyl, thienyl, thienothiazolyl,thienooxazolyl, thienoimidazolyl, thiophenyl and xanthenyl.

“Alkyl”, as used herein, refers to the radical of saturated orunsaturated aliphatic groups, including straight-chain alkyl, alkenyl,or alkynyl groups, branched-chain alkyl, alkenyl, or alkynyl groups,cycloalkyl, cycloalkenyl, or cycloalkynyl (alicyclic) groups, alkylsubstituted cycloalkyl, cycloalkenyl, or cycloalkynyl groups, andcycloalkyl substituted alkyl, alkenyl, or alkynyl groups. Unlessotherwise indicated, a straight chain or branched chain alkyl has 30 orfewer carbon atoms in its backbone (e.g., C₁-C₃₀ for straight chain,C₃-C₃₀ for branched chain), and more preferably 20 or fewer. Likewise,preferred cycloalkyls have from 3-10 carbon atoms in their ringstructure, and more preferably have 5, 6 or 7 carbons in the ringstructure.

“Alkylaryl”, as used herein, refers to an alkyl group substituted withan aryl group (e.g., an aromatic or heteroaromatic group).

“Heterocycle” or “heterocyclic”, as used herein, refers to a cyclicradical attached via a ring carbon or nitrogen of a monocyclic orbicyclic ring containing 3-10 ring atoms, and preferably from 5-6 ringatoms, consisting of carbon and one to four heteroatoms each selectedfrom the group consisting of non-peroxide oxygen, sulfur, and N(Y) whereY is absent or is H, O, (C₁₋₄)alkyl, phenyl or benzyl, and optionallycontaining 1-3 double bonds and optionally substituted with one or moresubstituents. Examples of heterocyclic ring include, but are not limitedto, benzimidazolyl, benzofuranyl, benzothiofuranyl, benzothiophenyl,benzoxazolyl, benzoxazolinyl, benzthiazolyl, benztriazolyl,benztetrazolyl, benzisoxazolyl, benzisothiazolyl, benzimidazolinyl,carbazolyl, 4aH-carbazolyl, carbolinyl, chromanyl, chromenyl,cinnolinyl, decahydroquinolinyl, 2H,6H-1,5,2-dithiazinyl,dihydrofuro[2,3-b]tetrahydrofuran, furanyl, furazanyl, imidazolidinyl,imidazolinyl, imidazolyl, 1H-indazolyl, indolenyl, indolinyl,indolizinyl, indolyl, 3H-indolyl, isatinoyl, isobenzofuranyl,isochromanyl, isoindazolyl, isoindolinyl, isoindolyl, isoquinolinyl,isothiazolyl, isoxazolyl, methylenedioxyphenyl, morpholinyl,naphthyridinyl, octahydroisoquinolinyl, oxadiazolyl, 1,2,3-oxadiazolyl,1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, oxazolidinyl,oxazolyl, oxindolyl, pyrimidinyl, phenanthridinyl, phenanthrolinyl,phenazinyl, phenothiazinyl, phenoxathinyl, phenoxazinyl, phthalazinyl,piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, piperonyl,pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl,pyrazolyl, pyridazinyl, pyridooxazole, pyridoimidazole, pyridothiazole,pyridinyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolinyl, 2H-pyrrolyl,pyrrolyl, quinazolinyl, quinolinyl, 4H-quinolizinyl, quinoxalinyl,quinuclidinyl, tetrahydrofuranyl, tetrahydroisoquinolinyl,tetrahydroquinolinyl, tetrazolyl, 6H-1,2,5-thiadiazinyl,1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl,1,3,4-thiadiazolyl, thianthrenyl, thiazolyl, thienyl, thienothiazolyl,thienooxazolyl, thienoimidazolyl, thiophenyl and xanthenyl.

“Heteroaryl”, as used herein, refers to a monocyclic aromatic ringcontaining five or six ring atoms consisting of carbon and 1, 2, 3, or 4heteroatoms each selected from the group consisting of non-peroxideoxygen, sulfur, and N(Y) where Y is absent or is H, O, (C₁-C₈)alkyl,phenyl or benzyl. Non-limiting examples of heteroaryl groups includefuryl, imidazolyl, triazolyl, triazinyl, oxazoyl, isoxazoyl, thiazolyl,isothiazoyl, pyrazolyl, pyrrolyl, pyrazinyl, tetrazolyl, pyridyl, (orits N-oxide), thienyl, pyrimidinyl (or its N-oxide), indolyl,isoquinolyl (or its N-oxide), quinolyl (or its N-oxide) and the like.The term “heteroaryl” can include radicals of an ortho-fused bicyclicheterocycle of about eight to ten ring atoms derived therefrom,particularly a benz-derivative or one derived by fusing a propylene,trimethylene, or tetramethylene diradical thereto. Examples ofheteroaryl can be furyl, imidazolyl, triazolyl, triazinyl, oxazoyl,isoxazoyl, thiazolyl, isothiazoyl, pyraxolyl, pyrrolyl, pyrazinyl,tetrazolyl, pyridyl (or its N-oxide), thientyl, pyrimidinyl (or itsN-oxide), indolyl, isoquinolyl (or its N-oxide), quinolyl (or itsN-oxide), and the like.

“Halogen”, as used herein, refers to fluorine, chlorine, bromine, oriodine.

The terms “alkenyl” and “alkynyl” refer to unsaturated aliphatic groupsanalogous in length and possible substitution to the alkyls describedabove, but that contain at least one double or triple bond respectively.

The terms ortho, meta and para apply to 1,2-, 1,3- and 1,4-disubstitutedbenzenes, respectively. For example, the names 1,2-dimethylbenzene andortho-dimethylbenzene are synonymous.

“Substituted”, as used herein, means that the functional group containsone or more substituents attached thereon including, but not limited to,hydrogen, halogen, cyano, alkoxyl, alkyl, alkenyl, cycloalkyl,cycloalkenyl, aryl, heterocycloalkyl, heteroaryl, amine, hydroxyl, oxo,formyl, acyl, carboxylic acid (—COOH), —C(O)R′, —C(O)OR′, carboxylate(—COO—), primary amide (e.g., —CONH₂), secondary amide (e.g., —CONHR′),—C(O)NR′R″, —NR′R″, —NR′S(O)₂R″, —NR′C(O)R″, —S(O)₂R″, —SR′, and—S(O)₂NR′R″, sulfinyl group (e.g., —SOR′), and sulfonyl group (e.g.,—SOOR′); where R′ and R″ may each independently be hydrogen, alkyl,alkenyl, alkynyl, cycloalkyl, aryl, heterocycloalkyl and heteroaryl;where each of R′ and R″ is optionally independently substituted with oneor more substituents selected from the group consisting of halogen,hydroxyl, oxo, cyano, nitro, amino, alkylamino, dialkylamino, alkyloptionally substituted with one or more halogen or alkoxy or aryloxy,aryl optionally substituted with one or more halogen or alkoxy or alkylor trihaloalkyl, heterocycloalkyl optionally substituted with aryl orheteroaryl or oxo or alkyl optionally substituted with hydroxyl,cycloalkyl optionally substituted with hydroxyl, heteroaryl optionallysubstituted with one or more halogen or alkoxy or alkyl or trihaloalkyl,haloalkyl, hydroxyalkyl, carboxy, alkoxy, aryloxy, alkoxycarbonyl,aminocarbonyl, alkylaminocarbonyl and dialkylaminocarbonyl, orcombinations thereof. In some instances, “substituted” also refers toone or more substitutions of one or more of the carbon atoms in a carbonchain (i.e., alkyl, alkenyl, cycloalkyl, cycloalkenyl, and aryl groups)which can be substituted by a heteroatom, such as, but not limited to, anitrogen or oxygen.

“Rubber,” or “Elastomer,” as used herein, refer to a crosslinked networkpolymer, which has viscoelastic properties.

As used herein, the term “network” refers to a three dimensionalsubstance having oligomeric and/or polymeric strands interconnected toone another by crosslinks.

As used herein, the term “prepolymer” refers to oligomeric or polymericstrands which have not undergone crosslinking to form a network.

As used herein, the term “crosslink” refers to a connection between twostrands. The crosslink may either be a chemical bond, a single atom, ormultiple atoms. The crosslink may be formed by reaction of a pendantgroup in one strand with the backbone of a different strand, or byreaction of one pendant group with another pendant group. Crosslinks mayexist between separate strand molecules, and may also exist betweendifferent points of the same strand.

“Curable,” as used herein, refers polymeric or oligomeric materials orcompositions thereof capable of being toughened or hardened typically bycross-linking of polymer and/or oligomer chains therein. “Curing,” asused herein refers to the process of applying an external stimulus, suchas, but not limited to, light, radiation, electron beams, heat, chemicaladditives, and combinations thereof which induce crosslinking to producetoughening or hardening of the materials.

The term “biocompatible”, as used herein, is intended to describematerials that do not elicit a substantial detrimental response in vivo.

As used herein, “biodegradable” polymers are polymers that degrade tooligomeric and/or monomeric species under physiological or endosomalconditions. In various preferred embodiments, the polymers and polymerbiodegradation byproducts are biocompatible. Biodegradable polymers arenot necessarily hydrolytically degradable and may require enzymaticaction to fully degrade.

“Catalysts” or “Catalytic centers,” as used herein, refer to a molecularspecies or component thereof which lowers the activation energy ofchemical reactions and is generally not destroyed or consumed by thechemical reaction and is or can be regenerated. Catalysts are often usedto increase rates or yields of chemical reactions and may offersignificant economic, efficiency and energy advantages to individuals orbusinesses that carry out these reactions.

“Viscosity,” as used herein refers to the resistance of a substance(typically a liquid) to flow. Viscosity is related to the concept ofshear force; it can be understood as the effect of different layers ofthe fluid exerting shearing force on each other, or on other surfaces,as they move against each other. There are several measures ofviscosity. The units of viscosity are Ns/m², known as Pascal-seconds(Pa-s). Viscosity can be “kinematic” or “absolute”. Kinematic viscosityis a measure of the rate at which momentum is transferred through afluid. It is measured in Stokes (St). The kinematic viscosity is ameasure of the resistive flow of a fluid under the influence of gravity.When two fluids of equal volume and differing viscosity are placed inidentical capillary viscometers and allowed to flow by gravity, the moreviscous fluid takes longer than the less viscous fluid to flow throughthe capillary. If, for example, one fluid takes 200 s to complete itsflow and another fluid takes 400 s, the second fluid is called twice asviscous as the first on a kinematic viscosity scale. The dimension ofkinematic viscosity is length²/time. Commonly, kinematic viscosity isexpressed in centiStokes (cSt). The SI unit of kinematic viscosity ismm²/s, which is equal to 1 cSt. The “absolute viscosity”, sometimescalled “dynamic viscosity” or “simple viscosity”, is the product ofkinematic viscosity and fluid density. Absolute viscosity is expressedin units of centipoise (cP). The SI unit of absolute viscosity is themilliPascal-second (mPa-s), where 1 cP=1 mPa-s. Viscosity may bemeasured by using, for example, a viscometer at a given shear rate.Additionally, viscosity may be measured by using, for example, aviscometer at multiple given shear rates. A “zero-shear” viscosity canthen be extrapolated by creating a best fit line of the fourhighest-shear points on a plot of dynamic viscosity versus shear rate,and linearly extrapolating viscosity back to zero shear. Alternatively,for a Newtonian fluid, viscosity can be determined by averagingviscosity values at multiple shear rates. Viscosity can also be measuredusing a microfluidic viscometer at single or multiple shear rates (alsocalled flow rates), wherein absolute viscosity is derived from a changein pressure as a liquid flows through a channel. Viscosity equals shearstress over shear rate. Viscosities measured with microfluidicviscometers can, in some embodiments, be directly compared to zero-shearviscosities, for example those extrapolated from viscosities measured atmultiple shear rates using a cone and plate viscometer.

The term “jettable”, as generally used herein, refers to curablesuitable for 3-dimensional inkjet printing applications.

As used herein, the terms “oligomer” and “polymers” each refer to acompound of a repeating monomeric subunit. Generally speaking, an“oligomer” contains fewer monomeric units than a “polymer.” Those ofskill in the art will appreciate that whether a particular compound isdesignated an oligomer or polymer is dependent on both the identity ofthe compound and the context in which it is used.

One of ordinary skill will appreciate that many oligomeric and polymericcompounds are composed of a plurality of compounds having differingnumbers of monomers. Such mixtures are often designated by the averagemolecular weight of the oligomeric or polymeric compounds in themixture. As used herein, the use of the singular “compound” in referenceto an oligomeric or polymeric compound includes such mixtures.

As used herein, reference to any oligomeric or polymeric materialwithout further modifiers includes oligomeric or polymeric materialhaving any average molecular weight.

“Mean particle size,” or “Average particle size,” as used herein,generally refers to the statistical mean particle size (diameter) of theparticles in a population of particles. The diameter of an essentiallyspherical particle may be referred to as the physical or hydrodynamicdiameter. The diameter of a non-spherical particle may referpreferentially to the hydrodynamic diameter. As used herein, thediameter of a non-spherical particle may refer to the largest lineardistance between two points on the surface of the particle. Meanparticle size can be measured using methods known in the art, such asdynamic light scattering.

Numerical ranges include, but are not limited to, ranges oftemperatures, ranges of pressures, ranges of molecular weights, rangesof integers, ranges of force values, ranges of times, ranges ofthicknesses, and ranges of gas flow rates. The disclosed ranges includevalues that such a range could reasonably encompass, as well assub-ranges and combinations of sub-ranges encompassed therein. Forexample, disclosure of a temperature range is intended to discloseindividually possible temperature values that such a range couldencompass, consistent with the disclosure herein. In another example,the disclosure that an annealing step may be carried out for a period oftime in the range of about 5 min to 30 min, also refers to time valuesthat can be selected independently from about 5, 6, 7, 8, 9, 10, 11, 12,13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, and30 minutes, as well as any range between these numbers (for example, 10min to 20 min), and any possible combination of ranges between thesetime values.

The term “about” or “approximately” as used herein generally meanswithin 20%, preferably within 10%, and more preferably within 5% of agiven value or range. The term “about x” further includes x.

II. Curable Formulations

In embodiments described herein, curable formulations of monomericand/or oligomeric precursors are formed via chemistries that enabledesirable material performance and tunable physical and thermomechanicalproperties to be obtained. Desirable material performance and tunablephysical and thermomechanical properties include, but are not limitedto, high toughness, optical clarity, high tensile strength, good solventresistance, good thermal resistance, tunable modulus, viscosity, tunableglass transition temperature, tunable cure time, and tunable surfaceadhesion. According to the embodiments described herein, materials,composites, and other compositions thereof can be formed from thecurable formulations.

The curable formulations include monomeric and/or oligomeric precursors.The monomeric and/or oligomeric precursors contain one or more reactivefunctional groups, where the one or more reactive functional groups canvary from n=1 to n=50, or greater, depending on the monomeric and/oroligomeric precursors. The curable formulations formed from monomericand/or oligomeric precursors can be tuned, for example, by varying thedegree of functionalization with one or more reactive functional groupsused to prepare the precursors and formulations thereof.

In some embodiments, the properties of the precursors can be tuned viathe inclusion of one or more moieties, such as cyclic aliphaticlinkages/linker groups for toughness, rigidity, UV resistance andthermal resistance; sterically hindered moieties and/or substituents,which can inhibit/control macromolecular alignment to afford amorphousmaterials, composites, and other compositions thereof uponpolymerization and which can afford high optical clarity.

In certain embodiments, the precursors of the formulation or mixtureinclude moieties and/or substituents that can form or contain linkages,such as urethane, amide, thiourethane and dithiourethane groups whichallow for inter-chain hydrogen bonding and can be used to impartincreased toughness and rigidity. In yet other embodiments, theselective incorporation of ester, beta-aminoester, carbonate, silylether linkages, or linker groups in the precursors can be used tocontrol environmental degradation time and solvent uptake, which canalso be tuned by incorporating pendant hydrophilic or hydrophobic groupsinto material compositions.

The precursors of the curable formulations can be prepared, for example,from mercapto, alkene, (meth)acrylate, alkyne, amine and epoxyfunctionalized monomeric and oligomeric constituents, or combinationsthereof. The stoichiometric ratios of monomeric and/or oligomericprecursors present in the curable formulations can be within the rangefrom about 1.00:4.00, about 1.00:3.00, about 1.00:2.20, about 1.00:2.00,about 1.00:1.00, about 1.00:0.97, about 1.00:0.95, about 1.00:0.90,about 1.00:0.50, about 1.00:0.33, about 1.00:0.25, and about 1.00:0.20.

The curable formulations formed of monomeric and/or oligomericprecursors can be cured by applying ultraviolent (UV) light, heat, acidor base catalyzed curing processes, or combinations thereof. The curedformulations are then subjected to performance characterization analysisand can be utilized, for example, in known additive manufacturingprocesses, such as stereolithography additive applications, and forcoatings applications.

Varying quantities of initiators or catalysts can be added to theformulations to catalyze addition reactions, between the monomericand/or oligomeric precursors, prior to or during the application of anoptional thermal aging process. Exemplary addition reactions include,but are not limited to, free radical initiated thiol-ene, base catalyzedMichael Addition and base catalyzed thiol-epoxy addition reactions.

For curable formulations designed to be UV curable, a photoinitiator canalso be added. For example, a free radical inhibitor can be added toacrylate containing formulations and select thiol-ene formulations.Exemplary photoinitiators include, but are not limited to,2,2-dimethoxy-2-phenylacetophenone (DMPA) anddiphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO). The amount ofphotoinitiator which can be added to form UV curable formulations can bewithin the range from about 0.001 wt % to 10 wt %. In some embodiments,the amount of photoinitiator added to the curable formulations can beabout 0.10 wt %, 0.20 wt %, 0.30 wt %, 0.40 wt %, 0.50 wt %, 1.00 wt %,1.50 wt %, 2.00 wt %, 2.50 wt %, 3.00 wt %, 3.50 wt %, 4.00 wt %, 4.50wt %, and 5.00 wt %. In some embodiments, free radical inhibitors (whichinclude, but are not limited to, 4-methoxyphenol and 1,4-hydroquinone)can be added to the curable formulations to a concentration in a rangefrom 0.01 to 2000 ppm. In some embodiments, the concentration of freeradical inhibitors added can be about 500 ppm, about 1000 ppm, or about1500 ppm. For curable formulations designed to be thermally curable,such as thiol-epoxy-based formulations, thermal free-radical initiatorsor tertiary amine catalysts can be added to catalyze curing. Exemplarythermal free-radical initiators include, but are not limited to, benzoylperoxide (BPO) and azobisisobutyronitrile (AIBN).Thermal free radicalinitiators catalyze radical initiated addition reactions, such as duringa thermal aging process, and the amounts added to the curableformulations can be within the range from about 0.001 wt % to 10 wt %.In some embodiments, the amount of thermal free radical initiator addedto the curable formulations can be about 0.10 wt %, 0.20 wt %, 0.30 wt%, 0.40 wt %, 0.50 wt %, 1.00 wt %, 1.50 wt %, 2.00 wt %, 2.50 wt %,3.00 wt %, 3.50 wt %, 4.00 wt %, 4.50 wt %, or 5.00 wt %. Tertiary aminebase catalysts can be used catalyze, for example, Michael Additionand/or thiol-epoxy reactions or related reactions, during thermal aging.The amounts of tertiary amine base catalyst(s) that can added to thecurable formulations can be in the range from about 0.01 wt % to 10 wt%. In some embodiments, the amount of tertiary amine base catalyst(s)which can be added to the curable formulations can be about 0.10 wt %,0.20 wt %, 0.30 wt %, 0.40 wt %, 0.50 wt %, 1.00 wt %, 1.50 wt %, 2.00wt %, 2.50 wt %, 3.00 wt %, 3.50 wt %, 4.00 wt %, 4.50 wt %, or 5.00 wt%.

Curing reactions can be used to fully cure or a substantially cure theformulations, wherein substantially refers to a percentage ofcrosslinking of at least about 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%,96%, 97%, 98%, or 99%.

In certain embodiments, the curable formulations are designed to bechemically curable using one or more chemical catalysts, such as acid orbase catalysts, to cure the curable formulation over a period of time.The one or more chemical catalysts can be added at concentrations ofabout 0.10 wt %, 0.20 wt %, 0.30 wt %, 0.40 wt %, 0.50 wt %, 1.00 wt %,1.50 wt %, 2.00 wt %, 2.50 wt %, 3.00 wt %, 3.50 wt %, 4.00 wt %, 4.50wt %, or 5.00 wt %. The time needed to achieve full curing will bedependent on the concentration of catalyst added and the nature of thecrosslinking reaction chemistries occurring in the formulation onstanding. In certain instances, such processes can be driven by applyingheat to the formulation.

Ceramic fillers can optionally be added to the formulations following athermal aging process. Examples include Cabot CAB-O-SIL TS-720, TS-610,TS-622, TS-530, EVONIK AEROSIL R8200, R106, R812S, R202, R208, R972,R974, R812S. In some embodiments, the amount of ceramic filler(s) addedcan be in the range of about 0.001 to 20.00 wt %. In some embodiments,the amount of ceramic filler(s) is about 0.50 wt %, 1.00 wt %, 1.50 wt%, 2.00 wt %, 2.50 wt %, 3.00 wt %, 3.50 wt %, 4.00 wt %, 4.50 wt %,5.00 wt %, 6.00 wt %, 7.00 wt %, 8.00 wt %, 9.00 wt %, or 10.00 wt %.Exemplary fumed silica additives include silica additives having anaverage particle size in the range of about 5 to 500 m²/g. In someembodiments, the fumed silica additives have an average particle size ofabout 50 m²/g, 75 m²/g, 100 m²/g, 120 m²/g, 150 m²/g, 200 m²/g, 250m²/g, 300 m²/g, or 350 m²/g.

Silanes can also be added to improve glass adhesion and adhesion tometals that include copper, zinc, iron, stainless steel, and aluminum.Examples include .vinylsilanes, mercaptosilanes, aminosilanes,methacrylosilanes added in 0.01 to 15 mole % equivalents to claimedformulations. Specific products: Evonik Dynasylan MTMO, AMMO, VTMO andEvonik (meth)acrylated silanes.

Modifiers can be added to the curable formulations before or afterapplying a curing and/or thermal aging processing step in order tomodify physical properties and/or curing profiles of the uncuredformulations, as well as the physical or thermomechanical properties ofcured formulations thereof. Exemplary modifiers include, but are notlimited to, trimethylolpropane tris(3-mercaptopropionate),pentaerithritol tetrakis(3-mercaptopropionate), dipentaerithritolhexakis(3-mercaptopropionate),tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, tetraethylene glycolbis(3-mercaptopropionate), 1,10-decanedithiol, ethylene glycolbis(3-mercaptopropionate), 1,2-ethanedithiol, 1,3-propanedithiol,1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol,2-mercaptoethanol, 2-hydroxyethylacrylate, 2-carboxyethylacrylate,acrylic acid, thioglycolic acid, iso-tridecyl 3-mercaptopropionate,sodium thioglycolate, butyl glycidyl ether, 2-ethylhexyl glycidyl ether,limonene oxide, limonene dioxide, dicyclopentadiene dioxide, castor oilglycidyl ether, 2-amino-2-methyl-1-propanol, vinyl cyclohexene oxide,allyl isothiocyanate, isophorone diisocyanate, bisphenol A ethoxylatediacrylate, bisphenol A ethoxylate diglycidyl ether, ethoxylatedtrimethylolpropane tris(3-mercaptopropionate), pentaerithritoltetrakis(polycaprolactone, mercaptopropionate terminated),polydimethylsiloxane, diglycidyl ether terminated, M_(n) 800, glyceroldiacrylate, glycerol triacrylate, and allyl glycidyl ether. In someembodiments, modifiers include sand, polymer powders, hydroxyapatitenanopowder, tungsten powder, metal powders, and ceramic powders.

In some embodiments, following a thermal aging step, the formulationscan be stored without degradation or without substantial degradation(i.e., less than about 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or1% change in the any one or more properties of the material, asdetermined by known testing methods) over a period of time of about 1day, to 5 days, to 10 days, to 20 days, to 30 days, to two months, threemonths, four months, five months, six months, one year, two years, threeyears, four years, five years, or longer.

In some embodiments, during or following a thermal aging step, theformulations can be mixed with one or more other curable formulations asdescribed herein. In yet some other embodiments, during or following athermal aging step the formulations can be mixed with one or moremodifiers as described herein.

In some embodiments, combinations of one or more curable formulationswith a cured material can be used to afford tunable viscosity,toughness, good biocompatibility, tunable biodegradation time inmultiple environments, unique and differentiating adhesion capabilitiesto selected substrate surfaces, advanced material capabilities,including but not limited to, shape memory and UV resistance.

In some embodiments, combinations of one or more curable formulationsand a modifier material can be used to afford tunable viscosity,toughness, good biocompatibility, tunable biodegradation time inmultiple environments, unique and differentiating adhesion capabilitiesto selected substrate surfaces, advanced material capabilities,including but not limited to, shape memory and UV resistance.

In certain embodiments, the curable formulations have a viscositybetween about 1.0 and 100.0 cP at about 20-25° C. In certainembodiments, the cured formulations alone or as composites furthercontaining one or more modifiers have a viscosity between about 10 and100.0 cP at about 20-25° C.

In certain embodiments, the cured formulations alone or as compositesthereof demonstrate stable viscosities that do not increase after about1 day, 5 days, 10 days, 20 days, 30 days, 40 days, 60 days, 70 days, 80days, 90 days, 100 days, or longer when stored at or near roomtemperature, optionally in light free conditions. In certain otherembodiments, the cured formulations alone or as composites thereofdemonstrate stable viscosities that do not increase when exposed toelevated temperatures of about 30° C. to 50° C., 30° C. to 60° C., 30°C. to 70° C., 30° C. to 80° C., 30° C. to 90° C., 30° C. to 100° C., or30° C. to 150° C. for periods of time of between 0.1 hours to 100 hours.

In certain embodiments, the curable formulations or cured formulationstherefrom, alone, as mixtures with other formulations, or containing oneor more modifiers are characterized by a Young's modulus between 0.01and 500.00 N/mm², preferably between 0.01 and 100.00 N/mm², morepreferably between 0.01 and 50.00 N/mm², even more preferably between0.01 and 10.00 N/mm², and especially preferably between 0.01 and 5.00N/mm². The Young's Modulus can be evaluated through mechanical testingsuch as compressive or tensile testing. The Young's Modulus can beevaluated using an Instron in tensile mode with uniaxial loading,testing a cast necked or dog-bone shaped sample. The Young's Modulus isevaluated by calculating the gradient of the linear region of theStress-Strain graph, where Young's Modulus E=σ/ε.

In certain embodiments, the curable formulations or cured formulations,alone, as mixtures with other formulations, or containing one or moremodifiers are characterized by a tensile strength between 0.01 and 5.00N/mm². The tensile strength of a dynamic network material may bedetermined by measuring the force required to break a material extendedin a unilateral direction by using an instrument such as an instron tocalculate force required to break a standardized shape such as a dogboneshaped material.

In certain embodiments, the dynamic network material is characterized bya crosslinking density between 1 and 75 mol/m³. The crosslinking densityof a dynamic network material may be determined by using the formulan=E/3RT, where E is the Young's Modulus evaluated from the tensile test,R is the ideal gas constant and T is temperature (298 K). In certainpreferred embodiments, the dynamic network material is characterized bya crosslinking density between 5-70 mol/m³, preferably, between 5-40mol/m³, and even more preferably between 5-20 mol/m³. In otherembodiments, the crosslinking density is between 1-15 mol/m³, preferablybetween 3-10 mol/m³, and especially preferably between 5-10 mol/m³. Inother embodiments, the crosslinking density is between 10-75 mol/m³,preferably between 10-65 mol/m³, even more preferably between 20-60mol/m³ and especially preferably between 30-50 mol/m³.

In some embodiments, the monomeric and/or oligomeric precursors includepolythiols which are formed, at least in part, from a reaction betweenC═C-containing compound(s) and SH-containing compounds. Such reactionsare often UV catalyzed but can also proceed under elevated temperatureconditions, is highly efficient, tolerant of many functional groups, andcapable of proceeding under mild conditions. (D. P. Nair, N. B. Cramer,T. F. Scott, C. N. Bowman, R. Shandas, Polymer, 2010, 51, 4383).

For example, the curable formulations can include one or more polythiolconstituents obtained from mercaptan-containing terpenes (such asD-Limonene and/or L-Limonene, and/or derivatives or analogs thereof)and/or terpenoids. Exemplary polythiols derived from terpenes orterpenoids include, but are not limited to, dipentene dimercaptan,isoprene dimercaptan, farnesene dimercaptan, farnesene trimercaptan,farnesene tetramercaptan, myrcene dimercaptan, myrcene trimercaptan,bisabolene dimercaptan, bisabolene trimercaptan, linalool dimercaptan,terpinolene dimercaptan, terpinene dimercaptan, geraniol dimercapan,citral dimercaptan, retinol dimercaptan, retinol trimercaptan, retinoltetramercaptan, beta-carotene polymercaptans, or combinations thereof.In some embodiments, the polythiols are derived from trimethylolpropanetrithiol, pentaerithritiol trithiol, pentaerithritol tetrathiol,inositol di-, tri-, tetra-, penta- and hexathiols.

In yet other embodiments, the curable formulations can include one ormore olythiol constituents obtained from mercaptan-containing cyclic,polycyclic, or linear aliphatic polyalkenes or alkynes. Exemplarypolythiols derived from these groups include, but are not limited to,trivinylcyclohexene dimercaptan, trivinylcyclohexene trimercaptan,dicyclopentadiene dimercaptan, vinylcyclohexene dimercaptan,triallylisocyanurate dimercaptan, triallyl isocyanurate trimercaptan,phenylhepta-1,3,5-triyne polmercaptans, 2-butyne-1,4-diol dimercaptan,propargyl alcohol dimercaptan, dipropargyl sulfide polymercaptans,dipropargyl ether polymercaptans, propargylamine dimercaptan,dipropargylamine polymercaptans, tripropargylamine polymercaptans,tripropargyl isocyanurate polymercaptans, tripropargyl cyanuratepolymercaptans.

In other embodiments, the curable formulations can include one or morepolythiol constituents obtained from mercaptan-containing, unsaturatedfatty acids or unsaturated fatty esters. Exemplary polythiols derivedfrom these groups include, but are not limited to, arachidonic aciddimercaptan, arachidonic acid trimercaptan, arachidonic acidtetramercaptan, eleostearic acid dimercaptan, eleostearic acidtrimercaptan, linoleic acid dimercaptan, linolenic acid dimercaptan,linolenic acid trimercaptan, mercaptanized linseed oil, mercaptanizedtung oil, mercaptanized soybean oil, mercaptanized peanut oil,mercaptanized walnut oil, mercaptanized avocado oil, mercaptanizedsunflower oil, mercaptanized corn oil, mercaptanized cottonseed oil.

The curable formulations can also include one or more alkeneconstituents such as, but not limited to, terpenes, terpenoids,dimerized terpenes or terpenoids, trimerized terpenes or terpenoids,oligomeric terpenes or terpenoids, polymerized terpenes or terpenoids,limonene, D-limonene, L-limonene, poly(limonene) having “n” repeat unitswherein “n” is greater than n=2 and less than 500,000, farnesene,myrcene, bisabolene, linalool, terpinolene, terpinene, geraniol, citral,retinol, beta-carotene, triallyl isocyanurate, 1,2,4-trivinylcyclohexane, norbornene functionalized poly(terpene) oligomers,norbornene-functionalized polydimethylsiloxane,norbornene-functionalized poly(butadiene), norbornene-functionalizedpolyisoprene oligomers, poly(isoprene) with having “n” repeat unitswherein “n” is 2 or more and less than 500,000, poly(butadiene) having“n” repeat units wherein “n” is 2 or more and less than 500,000, divinylether, triallylamine, diallylamine, diallyl bisphenol A,cyclohexanedimethanol diallyl ether, pentaerithritol tetraallyl ether,trimethylolpropane triallyl ether, 2,4,6-Triallyloxy-1,3,5-triazine,inositol diallyl ether, inositol triallyl ether, inositol tetraallylether, inositol pentaallyl ether, inositol hexaallyl ether, inositoldivinyl ether, inositol trivinyl ether, inositol tetravinyl ether,inositol pentavinyl ether, inositol hexavinyl ether, triallyl citrate,trivinyl citrate, 1,5-cyclooctadiene, 1,3-cyclooxtadiene,1,4-cyclooctadiene, 1,3-6 cyclooctatriene, cyclohexane diallyl ether,cyclohexane triallyl ether, cyclohexane tetraallyl ether, cyclohexanepentaallyl ether, cyclohexane hexaallyl ether, cyclohexane divinylether, cyclohexane trivinyl ether, cyclohexane tetravinyl ether,cyclohexane pentavinyl ether, cyclohexane hexavinyl ether,diclyclopentadiene, tricyclodecane dimethanol divinyl ether,tricyclodecane dimethanol diallyl ether, tricyclodecane dimethanol,norbornene capped, bicyclo[2.2.1]hepta-2,5-diene,norbornene-functionlized polyamide oligomers having “n” repeat unitswherein “n” is 2 or more polyamide repeat units and less than 100,000repeat units, allyl ether-functionlized polyamide oligomers having “n”repeat units wherein “n” is 2 or more polyamide repeat units and lessthan 100,000 repeat units, vinyl ether-functionalized polyamideoligomers having “n” repeat units wherein “n” is 2 or more polyamiderepeat units and less than 100,000 repeat units,norbornene-functionlized polydimethylsiloxane having “n” repeat unitswherein “n” is 2 or repeat units and less than 100,000 repeat units,allyl ether-functionlized polydimethylsiloxane having “n” repeat unitswherein “n” is 2 or repeat units and less than 100,000 repeat units,vinyl ether-functionlized polydimethylsiloxane having “n” repeat unitswherein “n” is 2 or repeat units and less than 100,000 repeat units,resorcinol diallyl ether, resorcinol divinyl ether, diallylamine,triallylamine, or allylamine.

The curable formulations can also include one or more acrylate ormethacrylate-based constituents such as, but not limited to, neopentylglycol diacrylate, glycerol diacrylate, glycerol triacrylate, ethyleneglycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropanetriacrylate, tris[2-(acryloyloxy)ethyl] isocyanurate, pentaerithritoltetraacrylate, pentaerithritol triacrylate, ethoxylatedtrimethylolpropane triacrylate, ethyoxylated pentaerithritoltriacrylate, ethoxylated pentaerithritol tetraacrylate,poly(dimethylsiloxane) diacrylate having “n” repeat units wherein “n” is2 or more repeat units and less than 500,000 repeat units,poly(isoprene) diacrylate having “n” repeat units wherein “n” is 2 ormore repeat units and less than 500,000 repeat units,poly(butadiene-co-nitrile) diacrylate having “n” repeat units wherein“n” is 2 or more butadiene repeat units and 2 or more nitrile repeatunits and less than 500,000 butadiene repeat units and less than 500,000nitrile repeat units, polyethyleneglycol diacrylate having “n” repeatunits wherein “n” is greater than 2 repeat units and less than 500,000repeat units, tricyclodecantedimethanol diacrylate, bisphenol Adiacrylate, ethoxylated bisphenol A diacrylate having “n” repeat unitswherein “n” is greater than 2 repeat units and less than 500,000 repeatunits, and methacrylated equivalents thereof of the above listedconstituents.

The curable formulations can also include one or more epoxy-basedconstituents such as, but not limited to, epoxidized terpenes orterpenoids, epoxidized dimerized terpenes or terpenoids, epoxidizedtrimerized terpenes or terpenoids, epoxidized oligomeric terpenes orterpenoids or polymerized terpenes or terpenoids, limonene oxide,limonene dioxide, poly(limonene oxide) having “n” repeat units wherein“n” is 2 or more repeat units and less than 500,000 repeat units,poly(isoprene oxide)-co-polyisoprene copolymers having “n” repeat unitswherein “n” is 2 or more repeat units and less than 500,000 repeatunits, poly(butadiene oxide)-co-polybutadiene copolymers having “n”repeat units wherein “n” is 2 or more repeat units and less than 500,000repeat units, epoxidized farnesene, epoxidized farnesene, epoxidizedmyrcene, epoxidized bisabolene, epoxidized linalool, epoxidizedterpinolene, epoxidized terpinene, epoxidized geraniol, epoxidizedcitral, epoxidized retinol, epoxidized beta-carotene, epoxidizedarachidonic acid, epoxidized eleostearic acid epoxidized linoleic acid,epoxidized linolenic acid, epoxidized linseed oil, epoxidized tung oil,epoxidized soybean oil, epoxidized peanut oil, epoxidized walnut oil,epoxidized avocado oil, epoxidized sunflower oil, epoxidized corn oil,epoxidized cottonseed oil, epoxidized palm oil, epoxidized glycerol,including glycerol diglycidyl ether and glycerol triglycidyl ether,epoxidized sorbitol, including sorbitol diglycidyl ether, sorbitoltriglycidyl ether, sorbitol tetraglycidyl ether, sorbitol pentaglycidylether and sorbitol hexaglycidyl ether, cyclohexanedimethanol diglycidylether, resorcinol diglycidyl ether, bisphenol A diglycidyl ether,hydrogenated bisphenol A diglycidyl ether, neopentyl glycol diglycidylether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidylether, tetraethylene glycol diglycidyl ether, polydimethylsiloxanediglycidyl ether, epoxidized butadiene oligomers, epoxidizedbutadiene-co-polynitrile oligomers, epoxidized grapefruit mercaptan,ethoxylated bisphenol A diglycidyl ether having “n” repeat units wherein“n” is 2 or more repeat units and less than 500,000 repeat units,ethoxylated hydrogenated bisphenol A diglycidyl ether having “n” repeatunits wherein “n” is 2 or more repeat units and less than 500,000 repeatunits, ethoxylated cyclohexanedimethanol diglycidyl ether having “n”repeat units wherein “n” is 2 or more repeat units and less than 500,000repeat units.

The curable formulations can also include one or more alkyne-basedconstituents such as, but not limited to, acetylene, supercriticalacetylene, propargyl alcohol, 2-butyne-1,4-diol,phenylhepta-1,3,5-triyne, dipropargyl sulfide, dipropargyl ether,propargylamine, dipropargylamine, tripropargylamine, tripropargylisocyanurate, tripropargyl cyanurate, propargyl inositol, dipropargylinositol, tripropargyl inositol, tetrapropargyl inositol, pentapropargylinositol, hexapropargyl inositol, dipropargylpiperazine, dipropargylcitrate, tripropargyl citrate, cyclohexanedimethanol propargyl ether,cyclohexanedimethanol dipropargyl ether, quinic acid lactone propargylether, quinic acid lactone dipropargyl ether, quinic acid lactonetripropargyl ether, tricyclodecanedimethanol propargyl ether,tricyclodecanedimethanol dipropargyl ether, bisphenol A bis(propargylether), hydrogenated bisphenol A bis(propargyl ether), cyclohexanedipropargyl ether, cyclohexane tripropargyl ether, cyclohexanetetrapropargyl ether, cyclohexane pentapropargyl ether, cyclohexanehexapropargyl ether, propargyl resorcinol, dipropargyl resorcinol.

In certain embodiments, the curable formulations once cured can haveunreacted, partially reacted, or fully reacted functional groups/substituents present therein. Exemplary functional groups include, but arenot limited to, thiol, alkene, alkyne, hydroxyl, carboxylic acid,acrylate, isocyanate, isothiocyanate, amine, epoxy, diene/dienophile,alkyl halide, carboxylic acid anhydride, aldehyde and phenol groups.

III. Methods of Making Curable and Cured Formulations

Methods for making the curable formulations, cured formulations thereof,and other composites thereof are described herein. In some embodiments,the methods are low waste methods which generally do not require any orany significant purification of the formulations, composites, orreaction products therein. The curable or cured formulations,composites, and other compositions thereof formed from the precursors asdescribed above and as shown in the examples generally proceed inadditive “one pot” steps. In some embodiments, these methods do notrequire the presence of any added solvents. In certain otherembodiments, the methods of making the formulations include use of oneor more aqueous or organic solvents, or combinations thereof which canbe removed, as needed.

In certain embodiments of the methods, a variety of building blockprecursors, as described above and in the examples, can be derived fromrenewable feedstocks, and these building blocks have reactive groups,such as, but not limited to thiols, amines, that allow them to undergoaddition reactions with reactive groups, such as C═C, present in otherbuilding blocks under appropriate reaction conditions. Such chemistriesinclude, but are not limited to, thiol-ene/thiol-yne/thiol-acrylatethermally induced free radical addition chemistry, which can be used tobuild molecular weight between thiol- andalkene/acrylate/alkyne-functionalized and epoxy-containing constituents.In certain embodiments, the reactions described herein can include aninitiator, such as, but not limited to, a thermal free radicalinitiator, such as AIBN, or a photoinitiator such as DMPA, which can beused in the presence of heat/UV to produce monomers, oligomers orpolymers which will not or are not cured products and will remain stableuntil additional reagents are added to induce curing. Curing reactionscan be used to form a fully crosslinked network polymer or asubstantially crosslinked network polymer, wherein substantially refersto a percentage of crosslinking of at least about 80%, 85%, 90%, 91%,92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99%. In other embodiments, basecatalyzed thiol-epoxy, thiol-acrylate, amine-epoxy and other similarreactions can afford alternative routes to constructingmonomers/oligomers/polymers as described herein. Other chemistries whichcan also be used to construct monomers/oligomers/polymers before curinginclude, but are not limited to, acrylate-amine and thiol-acrylateMichael Additions and isocyanate and isothiocyanate reactions withhydroxyl, thiol, amine and other related groups.

A non-limiting method of making a curable formulation includes the stepsof:

(a) mixing a polythiol constituent; an alkene-containing and/oralkyne-containing constituent; and an epoxy-containing constituent ,wherein the polythiol comprises at least three thiol groups; and

(b) thermally aging the mixture.

In some embodiments, the polythiol constituent is derived from amercaptan-containing terpene or terpenoid, a mercaptan-containing cyclicalkene, a mercaptan-containing polycyclic alkene, a linear alkene, amercaptan-containing alkyne, a mercaptan-containing unsaturated fattyacid, a mercaptan-containing unsaturated fatty ester, or amercaptan-containing polyalkene.

In some other embodiments, the polythiol constituent is derived fromtrimethylolpropane trithiol, pentaerithritiol trithiol, pentaerithritoltetrathiol, inositol, and dithiols, trithiols, tetrathiols, pentathiols,hexathiols, or combinations thereof.

In some embodiments, the mercaptan-containing terpene or terpenoid isdipentene dimercaptan, isoprene dimercaptan, farnesene dimercaptan,farnesene trimercaptan, farnesene tetramercaptan, myrcene dimercaptan,myrcene trimercaptan, bisabolene dimercaptan, bisabolene trimercaptan,linalool dimercaptan, terpinolene dimercaptan, terpinene dimercaptan,geraniol dimercapan, citral dimercaptan, retinol dimercaptan, retinoltrimercaptan, retinol tetramercaptan, beta-carotene polymercaptans, or acombination thereof.

In some embodiments, the mercaptan-containing cyclic alkene,mercaptan-containing polycyclic alkene, or linear aliphatic alkene istrivinylcyclohexene dimercaptan, trivinylcyclohexene trimercaptan,dicyclopentadiene dimercaptan, vinylcyclohexene dimercaptan,triallylisocyanurate dimercaptan, triallyl isocyanurate trimercaptan, ora combination thereof.

In some embodiments, the mercaptan-containing alkyne isphenylhepta-1,3,5-triyne polymercaptans, 2-butyne-1,4-diol dimercaptan,propargyl alcohol dimercaptan, dipropargyl sulfide polymercaptans,dipropargyl ether polymercaptans, propargylamine dimercaptan,dipropargylamine polymercaptans, tripropargylamine polymercaptans,tripropargyl isocyanurate polymercaptans, tripropargyl cyanuratepolymercaptans, or a combination thereof.

In some embodiments, the mercaptan-containing fatty acids or fatty acidesters are arachidonic acid dimercaptan, arachidonic acid trimercaptan,arachidonic acid tetramercaptan, eleostearic acid dimercaptan,eleostearic acid trimercaptan, linoleic acid dimercaptan, linolenic aciddimercaptan, linolenic acid trimercaptan, mercaptanized linseed oil,mercaptanized tung oil, mercaptanized soybean oil, mercaptanized peanutoil, mercaptanized walnut oil, mercaptanized avocado oil, mercaptanizedsunflower oil, mercaptanized corn oil, mercaptanized cottonseed oil, ora combination thereof.

In some embodiments, the alkene constituent is one or more of terpenes,terpenoids, dimerized terpene, dimerized terpenoids, trimerizedterpenes, trimerized terpenoids, oligomeric terpenes or terpenoids,polymerized terpenes, polymerized terpenoids, limonene, D-limonene,L-limonene, poly(limonene), farnesene, myrcene, bisabolene, linalool,terpinolene, terpinene, geraniol, citral, retinol, beta-carotene,triallyl isocyanurate, 1,2,4-trivinyl cyclohexane, norbornenefunctionalized poly(terpene) oligomers, norbornene-functionalizedpolydimethylsiloxane, norbornene-functionalized poly(butadiene),norbornene-functionalized polyisoprene oligomers, poly(isoprene),divinyl ether, triallylamine, diallylamine, diallyl bisphenol A,cyclohexanedimethanol diallyl ether, pentaerithritol tetraallyl ether,trimethylolpropane triallyl ether, 2,4,6-triallyloxy-1,3,5-triazine,inositol diallyl ether, inositol triallyl ether, inositol tetraallylether, inositol pentaallyl ether, inositol hexaallyl ether, inositoldivinyl ether, inositol trivinyl ether, inositol tetravinyl ether,inositol pentavinyl ether, inositol hexavinyl ether, triallyl citrate,trivinyl citrate, 1,5-cyclooctadiene, 1,3-cyclooxtadiene,1,4-cyclooctadiene, 1,3-6 cyclooctatriene, cyclohexane diallyl ether,cyclohexane triallyl ether, cyclohexane tetraallyl ether, cyclohexanepentaallyl ether, cyclohexane hexaallyl ether, cyclohexane divinylether, cyclohexane trivinyl ether, cyclohexane tetravinyl ether,cyclohexane pentavinyl ether, cyclohexane hexavinyl ether,diclyclopentadiene, tricyclodecane dimethanol divinyl ether,tricyclodecane dimethanol diallyl ether, tricyclodecane dimethanol,norbornene capped, bicyclo[2.2.1]hepta-2,5-diene,norbornene-functionlized polyamide oligomers, allyl ether-functionlizedpolyamide oligomers, vinyl ether-functionalized polyamide oligomers,norbornene-functionlized polydimethylsiloxane, allyl ether-functionlizedpolydimethylsiloxane, vinyl ether-functionlized polydimethylsiloxane,resorcinol diallyl ether, resorcinol divinyl ether, diallylamine,triallylamine, allylamine, or combinations thereof.

In certain embodiments, the alkene constituent is an acrylate ormethacrylate group, wherein the acrylate or methacrylate group isneopentyl glycol diacrylate, glycerol diacrylate, glycerol triacrylate,ethylene glycol diacrylate, tetraethylene glycol diacrylate,trimethylolpropane triacrylate, tris[2-(acryloyloxy)ethyl] isocyanurate,pentaerithritol tetraacrylate, pentaerithritol triacrylate, ethoxylatedtrimethylolpropane triacrylate, ethyoxylated pentaerithritoltriacrylate, ethoxylated pentaerithritol tetraacrylate,poly(dimethylsiloxane) diacrylate, poly(isoprene) diacrylate,poly(butadiene-co-nitrile) diacrylate, polyethyleneglycol diacrylate,tricyclodecantedimethanol diacrylate, bisphenol A diacrylate,ethoxylated bisphenol A diacrylate, or methacrylated equivalentsthereof.

In some embodiments, the alkyne constituent is acetylene, propargylalcohol, 2-butyne-1,4-diol, phenylhepta-1,3,5-triyne, dipropargylsulfide, dipropargyl ether, propargylamine, dipropargylamine,tripropargylamine, tripropargyl isocyanurate, tripropargyl cyanurate,propargyl inositol, dipropargyl inositol, tripropargyl inositol,tetrapropargyl inositol, pentapropargyl inositol, hexapropargylinositol, dipropargylpiperazine, dipropargyl citrate, tripropargylcitrate, cyclohexanedimethanol propargyl ether, cyclohexanedimethanoldipropargyl ether, quinic acid lactone propargyl ether, quinic acidlactone dipropargyl ether, quinic acid lactone tripropargyl ether,tricyclodecanedimethanol propargyl ether, tricyclodecanedimethanoldipropargyl ether, bisphenol A bis(propargyl ether), hydrogenatedbisphenol A bis(propargyl ether), cyclohexane dipropargyl ether,cyclohexane tripropargyl ether, cyclohexane tetrapropargyl ether,cyclohexane pentapropargyl ether, cyclohexane hexapropargyl ether,propargyl resorcinol, dipropargyl resorcinol, or combinations thereof.

In some embodiments, the epoxy-containing constituent is one or more ofepoxidized terpenes, epoxidized terpenoids, epoxidized dimerizedterpenes, epoxidized dimerized terpenoids, epoxidized trimerizedterpenes, epoxidized trimerized terpenoids, epoxidized oligomericterpenes, epoxidized oligomeric terpenoids, epoxidized polymerizedterpenes, epoxidized polymerized terpenoids, limonene oxide, limonenedioxide, poly(limonene oxide), poly(isoprene oxide)-co-polyisoprenecopolymers, poly(butadiene oxide)-co-polybutadiene copolymers,epoxidized farnesene, epoxidized farnesene, epoxidized myrcene,epoxidized bisabolene, epoxidized linalool, epoxidized terpinolene,epoxidized terpinene, epoxidized geraniol, epoxidized citral, epoxidizedretinol, epoxidized beta-carotene, epoxidized arachidonic acid,epoxidized eleostearic acid epoxidized linoleic acid, epoxidizedlinolenic acid, epoxidized linseed oil, epoxidized tung oil, epoxidizedsoybean oil, epoxidized peanut oil, epoxidized walnut oil, epoxidizedavocado oil, epoxidized sunflower oil, epoxidized corn oil, epoxidizedcottonseed oil, epoxidized palm oil, epoxidized glycerol, glyceroldiglycidyl ether, glycerol triglycidyl ether, epoxidized sorbitol,sorbitol diglycidyl ether, sorbitol triglycidyl ether, sorbitoltetraglycidyl ether, sorbitol pentaglycidyl ether and sorbitolhexaglycidyl ether, cyclohexanedimethanol diglycidyl ether, resorcinoldiglycidyl ether, bisphenol A diglycidyl ether, hydrogenated bisphenol Adiglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycoldiglycidyl ether, 1,4-butanediol diglycidyl ether, tetraethylene glycoldiglycidyl ether, polydimethylsiloxane diglycidyl ether, epoxidizedbutadiene oligomers, epoxidized butadiene-co-polynitrile oligomers,epoxidized grapefruit mercaptan, ethoxylated bisphenol A diglycidylether, ethoxylated hydrogenated bisphenol A diglycidyl ether,ethoxylated cyclohexanedimethanol diglycidyl ether, or combinationsthereof.

In some embodiments, the method of making the curable formulationincludes the addition of one or more modifiers to the mixture of step(a) prior to step (b) or during step (b), where the modifiers are one ormore of trimethylolpropane tris(3-mercaptopropionate), pentaerithritoltetrakis(3-mercaptopropionate), dipentaerithritolhexakis(3-mercaptopropionate),tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, tetraethylene glycolbis(3-mercaptopropionate), 1,10-decanedithiol, ethylene glycolbis(3-mercaptopropionate), 1,2-ethanedithiol, 1,3-propanedithiol,1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol,2-mercaptoethanol, 2-hydroxyethylacrylate, 2-carboxyethylacrylate,acrylic acid, thioglycolic acid, iso-tridecyl 3-mercaptopropionate,sodium thioglycolate, butyl glycidyl ether, 2-ethylhexyl glycidyl ether,limonene oxide, limonene dioxide, dicyclopentadiene dioxide, castor oilglycidyl ether, 2-amino-2-methyl-1-propanol, vinyl cyclohexene oxide,allyl isothiocyanate, isophorone diisocyanate, bisphenol A ethoxylatediacrylate, bisphenol A ethoxylate diglycidyl ether, ethoxylatedtrimethylolpropane tris(3-mercaptopropionate), pentaerithritoltetrakis(polycaprolactone, mercaptopropionate terminated),polydimethylsiloxane, diglycidyl ether terminated, glycerol diacrylate,glycerol triacrylate, allyl glycidyl ether, and combinations thereof.

In some other embodiments, the method of making the curable formulationincludes the addition of one or more modifiers to the mixture of step(a) prior to step (b) or during step (b), where the one or moremodifiers are sand, polymer powders, hydroxyapatite nanopowder, tungstenpowder, metal powders, ceramic powders, and combinations thereof.

In non-limiting embodiments, the thermal aging step (step (b)) includesthe application of heat to the mixture at a temperature in the rangebetween about 0° C. to about 150° C., 10° C. to about 100° C., 20° C. toabout 100° C., 20° C. to about 75° C. The thermal aging step can beapplied for a suitable period of time of between about 0.01 hours toabout 24 hours, about 0.01 hours to about 20 hours, about 0.01 hours toabout 15 hours, about 0.01 hours to about 10 hours, about 0.01 hours toabout 5 hours, about 0.01 hours to about 3 hours, about 0.01 hours toabout 2 hours, or about 0.01 hours to about 1 hours. In certaininstances, the thermal aging step includes the application of agitationto the mixture during all of step (b) or at least some portion of step(b).

In certain embodiments, following the thermal aging step the resultingcurable formulation can be stored.

According to certain embodiments, the curable formulations described areuncured as synthesized and additional chemicals can be added to allow orpromote curing and an additional step of curing (step (c)) is performed.In some embodiments, the mixture of step (a) further includes freeradical initiators, catalysts, or additives that can controllably (i.e.,by exposure to an external stimulus) induce or promote curing of theformulation. Exemplary curing processes include, but are not limited to,UV curing, electron beam curing, thermal curing capability, acid andbase catalyzed curing and polycondensation reactions. Curing reactionscan be used to form a fully crosslinked network polymer or asubstantially crosslinked network polymer, wherein substantially refersto a percentage of crosslinking of at least about 80%, 85%, 90%, 91%,92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99%. Such processes can generallyproceed in additive one-pot steps and do not require any purification orany significant purification after reaction completion. Exemplaryreactions which may occur during curing such as,thiol-ene/thiol-yne/thiol-acrylate, allyl, vinyl and other chemistriesallow for reactions to occur under UV, e-beam, and thermally drivenreaction conditions, thiol-epoxy, thiol-acrylate, amine-epoxy, as wellas other base-catalyzed reactions that can be processed with or withoutheating, Michael additions that include acrylate-amine andthiol-acrylate reactions, isocyanate and isothiocyanate reactions withhydroxyl, thiol, amine and other groups. In a UV-based curing step,irradiation energies ranging from 0.15 mJ/cm² to 5.0 J/cm² for a periodof time in the range of 0.01 seconds to 1 hour can be applied to thecurable formulations or mixtures thereof containing a suitablephotoinitiator.

According to certain other embodiments, the curable formulationsdescribed are uncured as synthesized and additional chemicals can beadded to allow or promote curing upon standing for a period of time. Itis believed that the addition of chemical agents, such as acid or basecatalysts, can promote crosslinking chemistries which result in a curedmaterial over time. As will be appreciated by one skilled in the art thetime required to achieve complete or high degree of curing (such as >90%curing) will depend on the amount of chemical agents added and thenature of the reaction chemistries which occur in the formulation.

IV. Methods of Using Curable Formulations and Articles of ManufactureThereof

The curable formulations can be used in new methods of manufacture.Methods that are used to manufacture materials from the curableformulations are significantly influenced by material processingcapability, and processing capability often refers to a material'sability to be successfully and efficiently subjected to various methodsof manufacture.

The curable formulations and cured formulations thereof described hereincan also be used in processes for fabricating articles from thesecompositions, and articles fabricated from these compositions.

In some embodiments, the curable formulations can be used to form filmsand/or slabs on substrates using known techniques. In a non-limitingembodiment, a thermally or chemically curable formulation or mixturethereof can be deposited into a mold and cured at a temperature in therange of about 10° C. to about 150° C., 20° C. to about 130° C., 20° C.to about 120° C., 20° C. to about 100° C., 20° C. to about 75° C., 20°C. to about 50° C. The curing time applied may be from about 10 secondsto 10 days, 10 seconds to 5 days, 10 seconds to 3 days, 10 seconds to 2days, 10 seconds to 1 day, 10 seconds to 10 hours, 10 seconds to 5hours, 10 seconds to 1 hours, 10 seconds to 50 minutes, 10 seconds to 40minutes, 10 seconds to 30 minutes, 10 seconds to 20 minutes, 10 secondsto 10 minutes, 10 seconds to 5 minutes, 10 seconds to 4 minutes, 10seconds to 3 minutes, 10 seconds to 2 minutes, or 10 seconds to 1minute.

In some embodiments, composites can be formed from the curableformulations by addition of modifiers and/or fillers as described above.In a non-limiting embodiment, a curable formulation or mixture thereofcan be mixed with a modifier and/or filler (i.e., fumed silica) toproduce a mixture or dispersion which is then cured under appropriateconditions as described herein. The mixtures can also be used as inksfor printing processes as described below.

Curable formulations, mixtures thereof, and composites thereof (whichcontain modifiers and/or fillers) can be used as inks for a variety ofprinting applications, such as 3-D printing. In one embodiment, aprinting method can include the steps of:

(a) printing a thermally aged curable formulation including a polythiolconstituent; an alkene-containing and/or alkyne-containing constituent;and an epoxy-containing constituent; and

(b) curing the printed formulation

wherein the curing step is performed simultaneously with the printing ofthe thermally aged curable formulation of step (a).

In such embodiments, the thermally aged curable formulation furtherincludes an initiator or catalyst which can be decomposed by an externalstimulus (i.e., light or heating) to induce curing. In such embodiments,the printing can performed using known techniques such as, but notlimited to, stereolithographic additive printing, dynamic lightprojection printing, an inkjet printing apparatus, a photojet printing,or a direct write process.

In certain 3-D printing embodiments, the printing step includes jettingthe thermally aged curable formulation into one or more powders such assand, polymer powders, hydroxyapatite powders, and tungsten powderswhich then harden into powder-rich composite materials. Hardening timecan be tuned by varying the amount of initiator or catalystconcentration in the formulation). Composite materials with geometricconfigurations patterned by inkjet deposition can also be cured aroundpowder particles and then removed from the powder-containing glasstrays. These patterned composites could then be built upon by furtherprinting (for 3-D inkjet additive manufacturing process) if desiredand/or subsequently utilized in a wide number of processing techniques,including the following exemplary processes:

-   -   (a) Polymer Powder Sintering: Heating above polymer powder T_(g)        or T_(m) or subjection to solvent fumes to fuse polymer        particles    -   (b) Casting: Pouring hardening liquid (e.g., investment) around        patterned composite, allowing poured liquid to harden and then        burning out polymeric composite to afford a mold with a negative        image of original inkjet patterned geometry, which can be used        to manufacture metals (e.g., investment casting, foundry        production, etc.)    -   (c) Ceramic/Metal Sintering: Heating patterned composites to        sufficient temperatures to fuse ceramic or metal particles and        burn out cured thiol-epoxy polymeric binder constituents.

The advantages of the jettable formulations include the lower toxicitiesof uncured formulations, as compared to analogous resins likefuran-based resins and certain phenolic resins, the excellent wetting toa number of substrates after jetting (wetting is hypothesized to be inpart facilitated by sulfur constituency), tunable cure time based oncatalyst concentration for powder/catalyst blends onto which resins werejetted, and superior stability in comparison with other epoxy basedresins (for example, an epoxy-amine control resin comprised of neopentylglycol diglycidyl ether and xylylene diamine underwent a substantialviscosity increase at 20° C. only 1-2 h after mixing of epoxy and amineconstituents and was consequently shown to be unsuitable for inkjetprocessing). Additional polythiol monomers that are hypothesized to beideal for the formulation of low viscosity, epoxy-stable, jettablethiol-epoxy resins include pentaerithritol tetrathiol, farnesenetetrathiol, 1,2,4-trivinylcyclohexanetrimercaptan, linalool dimercaptanand inositol hexathiol.

In yet other embodiments, curable formulations or mixtures thereof,neat, or dissolved or dispersed in water and/or organic solvent) can beapplied to a substrate material including, but not limited to, materialsmade of wood, wire, glass, aluminum, steel, zinc, iron, other metals,metal alloys, ceramics, or combinations thereof, as one or morecoatings. The one or more coatings alone or together may be applied toafford a thickness varying from about 0.01 micron to 500 microns, about0.01 micron to 300 microns, or about 0.01 micron to 100 microns.Exemplary methods including, but not limited to, roll coating, spraycoating, brush coating and hot melt coating techniques. Forsolvent/water dissolved/dispersed coatings, a drying time can be appliedwhich is between 0.1 min and 5 days. For 100% solids UV curablecoatings, full or partial curing can be induced by exposure toirradiation energies ranging from 0.15 mJ/cm² to 5.0 J/cm² for a periodof time in the range of 0.01 seconds to 1 hour.

EXAMPLES Example 1 Synthesis and Analysis of Expanded Polystyrene FoamProcedure for GPC Analysis of EPS

Gel permeation chromatography (GPC) measurements were conducted onexpanded polystyrene foam (EPS) samples taken from a series of EPS cupspurchased from Chick-fil-A, Inc. A tetrahydrofuran GPC system equippedwith a Waters Chromatography (Milford, Mass.) model 1515 isocratic pump,a model 2414 differential refractometer, and a three-column set ofPolymer Laboratories (Amherst, Mass.) Styragel columns (PLgel 5 μm MixedC, 500 Åand 104 Å, 300.sub.-7.5 mm columns). The system was equilibratedat 35° C. in tetrahydrofuran, which served as the polymer solvent andeluent (flow rate set to 1.00 mL/min). Polymer solutions were preparedat a known concentration (about 3 mg/mL), filtered with a 0.2 micronPTFE mesh filter, and an injection volume of 200 μL was used. Datacollection and analyses were performed with Precision Acquire softwareand Discovery 32 software (PrecisionDetectors). The differentialrefractometer was calibrated with standard polystyrene materials (SRM706 NIST). The corresponding molecular weight data are provided in Table1 below.

TABLE 1 Molecular weight data for GPC trace of EPS sample Mn (Da) Mw(Da) Polydispersity Index 150200 395800 2.635

Procedure for EPS Solubility Experiments:

20 small EPS cups purchased from Chick-fil-A, Inc. were massed, and theaverage mass data and standard deviation is provided in Table 2.

TABLE 2 Average EPS cup weight and standard deviation for 20 EPS cupspurchased from Chick-fil-A ®, Inc. Avg Cup Weight (g) Standard Deviation5.415 0.074The data in Table 2 were used to calculate the solubility of the cups invarious solvents in cups/gallon. EPS cups were broken down in aprofessional grade blender to a fine powder, washed with water, anddried in an oven at 100° C. over three days. The powder was used for gelpermeation chromatography (vide supra) and solubility tests. EPSsolubility tests were conducted for dichloromethane, d-limonene,styrene, ethyl acetate, acetone, petroleum ether, and gasoline (87octane rating). 5 mL of each solvent was measured and poured into a 20mL dram vial with a PTFE stir bar. Each vial was sealed and weighedbefore any polystyrene was added. The vials remained sealed duringduration of the experiments except for the time of each EPS addition toprevent solvent evaporation. A small amount of EPS was added to eachvial (about 50 mg) and allowed to stir until completely dissolved.Dissolution was aided by vortexing. After each iteration of EPSaddition, the solutions were assessed for EPS saturation. EPS additionwas terminated when deemed saturated, either when no more EPS would gointo solution or until the mixture viscosity prevented stir barmovement. Vials were then weighed to calculate the amount polymer addedand each respective EPS solubility. The results of the solubilitystudies are provided in Table 3.

TABLE 3 Solubility study results for EPS samples taken from Chick-fil-Afoam cups for various solvents. Solubility data are provided incups/gallon solvent Solvent Cups/Gallon Acetone <77.20 Dichioromethane474.44 Ethyl Acetate 447.63 Gasoline (87 Octane) <155.71 Limonene 423.10Petroleum Ether <11.2 Styrene 405.37

Dichloromethane and ethyl acetate dissolved the largest amount of EPS,and more polar solvents were not as successful at dissolving similaramounts of polymer (acetone, petroleum ether). D-limonene and styrenealso performed well, dissolving nearly as much as dichloromethane andethyl acetate. 87 octane gasoline was a poor solvent choice fordissolving EPS. Very little of the EPS went into solution, and instead,the EPS mainly swelled. This behavior remained consistent even after oneday of stirring at 25° C. The same also occurred for acetone andpetroleum ether.

Procedure for Demonstrating Extraction Based Purification of EPS CupContaining 100 mL Coca-Cola®:

100 mL of Coca-Cola® was poured from an unopened can into a 250 mL glassbeaker. The Coca-Cola® was then poured from the glass beaker into asmall EPS cup purchased from Chick-fil-A, Inc. 200 mL d-limonene, whichwas purchased from TCI America, was also poured into a 500 mL glassbeaker. The beaker containing the d-limonene was placed on a stir plateat 25° C., and a PTFE stir bar was added. The EPS cup containing the 100mL Coca-Cola® was then inserted in the beaker that contained the 200 mLd-limonene, and the solution was stirred at a stir setting of 2 (out of10). After 20-30 seconds, the cup began to dissolve, and after 45seconds, the cup burst open, and the Coca-Cola® spilled into the beakerof d-limonene. The EPS cup was stirred in the d-limonene/Coca-Cola®mixture for an additional 4 min, after which it was determined to becompletely dissolved. Upon turning off the stirring of the solution, twoimmiscible layers immediately were observable in the 500 mL beaker: thetop layer consisted of the EPS cup dissolved in d-limonene, and thebottom layer consisted of Coca-Cola®

Procedure for EPS Reclamation by Curing d-Limonene/EPS Solution UsingUV-Catalyzed Thiol-Ene Free Radical Addition:

Using a syringe, 5 mL of the top layer of the two-layer mixturedescribed above that resulted from dissolution of a Coca-Cola®containing EPS cup into D-limonene was placed in a 20 mL glass vial.Based on the initial mass of the EPS cup and the initial volume oflimonene to which the cup was added, a PS concentration of 26.1 mgEPS/mL limonene was assumed, and mass of limonene in the solution, whichhas a C.dbd.C functionality of 2, was calculated accordingly. Astoichiometric amount of the tetrathiol pentaerythritoltetrakis(3-mercaptopropionate) (PETMP) was added to the solution to givea C.dbd.C:SH ratio of 1:1. 1 wt % of the photoinitiator2,2-dimethoxy-2-phenylacetophenone (DMPA) was also added to thesolution. The PETMP was not initially miscible with the d-limonene/EPSsolution; however, upon exposure to 365 nm UV light in a UVP CL-1000 UVCrosslinking Chamber for 20 seconds, the mixture increased in viscosityand eventually became completely clear. The viscous solution was thenpipetted out of the glass vial and injected between two 2″×3″ glassmicroscope slides separated by two 1 mm-thick glass spacers and heldtogether using binder clips. The glass slides containing the injectedsolution were then placed in the UVP Crosslinking Chamber, exposed to365 nm UV light for 30 min, and subsequently removed from the chamber.Upon separation of the glass slides, an elastomeric film with sufficientmechanical integrity to handle was observed to have formed. The film waspost-cured at 120° C. at 1 torr for 12 hours, after which it wasremoved, handled, and subjected to thermo-mechanical characterizationexperiments. Because the EPS composition in this mixture was very low inthis example (<0.5 wt %), minimal phase separation was observed in theresulting rubber.

Dynamic Mechanical Analysis:

4 mm×30 mm×1.0 mm rectangular samples for dynamic mechanical analysis(DMA) were machined using a Gravograph LS100 40 W CO2 laser machiningdevice. DMA was performed using a TA Instruments Q800 Dynamic MechanicalAnalyzer in the DMA Multifrequency/Strain mode in tension using adeformation of 0.1% strain, a frequency of 1 Hz, a force track of 150%,and a preload force of 0.01 N. Each experiment was run from −50 to 100°C. using a heating rate of 2° C./min. DMA results demonstrated that thePETMP and d-limonene monomers reacted in the presence of UV light toform a thermoset network with a rubbery modulus of approximately 4.2MPa.

Example 2 Synthesis of Polystyrene Compositions

Polymer Synthesis:

Functional equivalents totaling 10 g of D-limonene (TCI America, >95%,)trimethylolpropane tris(3-mercaptopropionate), pentaerithritoltetrakis(3-mercaptopropionate) (Sigma Aldrich, >95%), and/ordipentaerithritol hexakis(3-mercaptopropionate) (Wako, >97%) were massedin glass vials, and 1 wt % 2,2′-dimethoxy-2-phenylacetophenone (DMPA)(Sigma Aldrich, >99%) photoinitiator was added. EPS powder, which wasground from EPS cups provided by Chick-fil-A, Inc. (CFA), was added tothe monomer mixtures in varying quantities so as to formulate mixtureswith polystyrene compositions of 0, 10, 20, and 30% overall weightfraction. The monomer and EPS mixtures were not miscible initially andwere heated to 140° C. for 2 hours, after which the formation ofhomogeneous solutions occurred. The resulting solutions exhibitedviscosity increases with increasing EPS composition. Neat films werecast by injecting the hot solutions inside glass molds pre-heated to140° C. The injections were carried out inside a vacuum oven heated to140° C. The hot glass molds were then immediately removed from the oven,placed in a UVP CL-1000L 365 nm UV Crosslinking Chamber, and exposed to365 nm UV irradiation for 1 hour. Within 10-20 seconds of UV exposure,the clear homogeneous solutions inside the glass molds began to turnwhite, apparently undergoing polystyrene phase separation brought on byeither poly(thioether) network formation, cooling temperatures, or bothfactors. The resulting films became completely white within 1-2 min.After 1 h, the cured films were post-cured at 130° C. at 1 torr for 24hours. Without polystyrene, the poly(thioether) networks were amorphous,optically clear rubbers, and the addition of PS resulted in theformation of opaque materials.

Microstructural Imaging by Scanning Electron Microscopy:

SEM imaging was used to understand the effects of increasing PScomposition on microstructural morphology. SEM samples were prepared byimmersion of ˜100 mg samples in liquid nitrogen for 30 s, coldfracturing by hand, attempted thermoplastic PS phase extraction byimmersion of fractured ˜50 mg samples in 100 mL dicholoromethane andlight vortexing for 48 hr. using a LabConco RapidVap® apparatus atvortex setting 15 and at ambient temperature and pressure, drying ofDCM-swelled samples at 50° C. at 1 torr for 48 h, and gold sputteringwith a Cressington 108 sputter coater, model 6002-8 (Ted Pella, Inc.,Redding, Calif.) for 60 s at a height of 3 cm, prior to imaging. Allsamples were imaged on the fractured faces at 25, 500, and 3000×magnification using a Hitachi TM3000 Tabletop Microscope (Hitachi HighTechnologies America, Inc. Nanotechnology Systems Division, Dallas,Tex.), with a filament current set to 1750 mA. Software used to acquirethe images was Bruker Quantax 70 Microanalysis Software package (BrukerNano GmbH, Berlin, Germany).

Atomic Force Microscopy:

AFM micrographs of the system were taken with an Asylum 3D-SA atomicforce microscope operated in tapping mode at 142 kHz, a nominal drivevoltage of 500 mV. A silica nitride probe was used with k=40 N/m (VistaProbes) and a nominal tip diameter of 10-15 nm as reported by themanufacturer. Sample preparation included a fast rinse of the samples(0%, 10%, 20% and 30% PS) with a 25% by volume aqueous ethanol solution(<5 seconds) followed immediately by drying under a dry, filterednitrogen gas flow for ca. 10 minutes and fixture to a glass slide.

Dynamic Mechanical Analysis:

DMA experiments were performed on triplicate samples using a TAInstruments Q800 Dynamic Mechanical Analyzer in the DMAMultifrequency/Strain mode in tension using a deformation of 0.1%strain, a frequency of 1 Hz, a force track of 150%, and a preload forceof 0.01 N. Each experiment was run from −50 to 150° C. using a heatingrate of 2° C./min on 4.0×25.0×0.75 mm rectangular samples, which weremachined using a Gravograph LS100 40 W CO₂ laser machining instrument.

Uniaxial Tensile Testing:

ASTM Type V dog bone samples were machined using a Gravograph LS100 40 WCO₂ laser machining device. All laser machined samples except for therubbery 0% PS samples were sanded around the edges using 400, 800 gritsandpaper. Strain-to-failure experiments were conducted at 25° C. in atemperature chamber that utilizes forced convection heating on 0% and30% samples synthesized in this study and on 100% PS samples(McMaster-Carr, Mw-350 kDa) on n5 specimens for each sample. Theexperiments were conducted using an Instron Model 5965electromechanical, screw driven test frame equipped with a 500 N loadcell and 1 kN high temperature pneumatic grips. An Instron AdvancedVideo Extensometer with a 60 mm field-of-view lens optically measuredthe deformation of the samples by tracking parallel lines applied at theends of the gauge length. The samples were heated to 25° C. under zeroload (unclamped bottom grip). The temperature was held for 10 min toallow for thermal equilibrium to be reached, after which the bottom gripwas clamped, and then experiments were started thereafter using adeformation rate of 10 mm/min. Data were recorded using Instron Bluehill3 software.

Shape Memory Characterization:

To determine percent recoverable strain for select samples, shape memorycharacterization experiments were performed using a TA Instruments Q800DMA on laser machined 25.0×4.0×0.4 mm rectangular specimens. In the DMAStrain Rate Mode in tension, rectangular specimens were heated to Tg+25°C. (glass transitions, either for the poly(thioether) rubber networks orfor polystyrene) were determined by the peak of the tangent deltas fromthe previous DMA results), allowed to equilibrate for 30 min, and thenstrained to deformations of 25%. The strained samples were then cooledto T_(g)−50° C. and allowed to equilibrate for an additional 30 min. Forfree strain recovery experiments, which were used to measure the percentrecoverable strains of the

SMPs, the drive force was set to zero after equilibration at Tg−50° C.,the samples were re-heated to T_(g)+50° C. at 2° C./min, and the freestrain recovery experiments were repeated over four or five cycles. Theamount of recoverable deformation was recorded using TA InstrumentsQSeries software and analyzed using TA Instruments Universal Analysissoftware.

Silica Filled Composite Synthesis:

Functional equivalents totaling 10 g of D-limonene (TCI America, >95%,)trimethylolpropane tris(3-mercaptopropionate), pentaerithritoltetrakis(3-mercaptopropionate) (Sigma Aldrich, >95%), and/ordipentaerithritol hexakis(3-mercaptopropionate) (Wako, >97%) were massedin glass vials, and 1 wt % 2,2′-dimethoxy-2-phenylacetophenone (DMPA)(Sigma Aldrich, >99%) photoinitiator was added. The mixtures weresonicated at 40° C. until the DMPA dissolved in the TMPTMP layer.Heating the immiscible mixtures to 100° C. for 3 min resulted in theformation of a homogeneous solution, which remained homogeneous aftercooling to 25° C. The cooled solution was then added in 5 g quantitiesto FlackTek Max 15 polypropylene mixer cups. To one cup, untreatedsilica gel (Sigma Aldrich Corporation, ˜63.0 μm average particle size)was added, and to another cup, fumed silica (Sigma Aldrich Corporation,0.2-0.3 μm average particle size) was added. The mixtures were mixed at1600 rpm for 30 s in a FlackTek DAC 150 FVZ-K Speedmixer, and theresulting monomer/silica mixes appeared to be well-mixed. Thesilica-containing mixtures were then transferred to glass moldsseparated by 1 mm-thick spacers, cured using 365 nm UV light for 45 minand post-cured at 120° C. for 24 h at 1 torr. The resulting reinforcedthiol-ene composited exhibited significantly increased mechanicalintegrity in comparison with unfilled analogs.

Example 3 Manufacture Cell Phone Case

Molded Prototype Cell Phone Case Prototype Fabrication:

Structures and articles of manufacture were also demonstrated by theconstruction of an IPHONE 4® protective case prototype molded from thedissolved product described above. The homogenous mixture describedabove consisting of D-limonene-co-TMPTMP with 30% PS was molded with UVcure (365 nm) for one hour at 25° C. This prototype case demonstratesthe ease with which the material described herein may be processed intouseful products for potential industrial application.

A positive mold with geometric dimensions approximately representativeof those of a protective case made to fit an APPLE IPHONE 4® cellulardevice was designed using SolidWorks software. Using a Stratasys Fortus360 mc 3D printer, positive molds were printed using the Stratasysbase-soluble resin. Each printed positive molds was then placed inpre-assembled 2″×6″×4″ acrylic molds and attached to the bottom of themold using super glue. Pre-mixed silicone Sylgard 184® base and curingagent were then poured over the printed molds and evacuated at 1 torr at25° C. for 5 min, after which a smooth surface layer was observed. Thesilicone mold was then cured at 50° C. for 4 h. The printed resin wasdissolved out of the silicone mold by etching in 0.1 N NaOH solutionusing the Stratasys base bath for 72 h. The resulting silicone moldcontained a negative image of an APPLE PHONE 4® case. This silicone moldand 50 g of functional equivalents of limonene and TMPTMP with 30 wt %PS additive were pre-heated to 140° C. for 2 h. The dissolved PSsolution was then poured in the oven into the silicone mold. The moldedsolution was then moved into a UVP CL-1000L 365 nm UV crosslinkingchamber, exposed to UV irradiation for 1 h, and post-cured at 130° C. at1 torr for 24 hours.

The mixture changes in optical behavior from transparency to opacity asthe PS content heterophase increases in the D-limonene-co-polythiolnetworks. D-limonene-co-TMPTMP films containing 0% and 30% PS additivesgo from nearly transparent to opaque.

Processable Putty Preparation:

Functional equivalents totaling 10 g of D-limonene (TCI America, >95%,)trimethylolpropane tris(3-mercaptopropionate), pentaerithritoltetrakis(3-mercaptopropionate) (Sigma Aldrich, >95%), and/ordipentaerithritol hexakis(3-mercaptopropionate) (Wako, >97%) were massedin glass vials, and 1 wt % 2,2′-dimethoxy-2-phenylacetophenone (DMPA)(Sigma Aldrich, >99%) photoinitiator was added. EPS powder, which wasground from EPS cups provided by Chick-fil-A, Inc. (CFA), was added tothe monomer mixtures in varying quantities so as to formulate mixtureswith polystyrene compositions of 0, 10, 20, and 30% overall weightfraction. The monomer and EPS mixtures were not miscible initially andwere heated to 140° C. for 2 hours, after which the formation ofhomogeneous solutions occurred. The homogeneous mixtures were thencooled to 25° C. and subsequently exhibited transitions fromtransparency to opacity. The opaque, uncured products were soft,putty-like resins that could be molded into desired geometries andsubsequently cured either at 25° C. or by re-heating to elevatedtemperatures in the range of 140 to 180° C. to re-afford homogeneoussolutions, which could then be molded into desired geometries and UVcured. The “putty” like product claimed herein is a metastableall-in-one A+B resin that could be packaged as such and sold as acommercial product fur subsequent curing at a later, desired time.

Processable Putty as a 3D Printable Ink:

The processable putty was molded from an undefined geometric state intoa spherical geometric state using applied shear stress/pressure at 25°C. When shear stress/pressure was applied, the putty resin began toflow. Upon removal of the applied shear stress/pressure, the putty resinceased flowing and maintained the geometry into which it was processed.In this experimental example, the polystyrene precipitated phases act asfillers that stabilize resin mixtures and afford a rheological profilethat includes a yield stress, above which flow occurs and below whichprocessed geometry is maintained. Such rheological behavior isconsistent with that of a 3D printable or otherwise moldable resin, andupon printing a putting resin the resin could be cured using UV light tofix printed geometries.

Silica Reinforcement as a Route to 3D Printable Rheology:

Approximately 1 g of each of the silica-containing monomer mixtures wereremoved from the FlackTek Max 15 cups after mixing using a spatula andwere transferred to 3 mL polypropylene syringes fitted with 18 gaugeneedles. Both the unmodified and fumed 10% silica-containing samplesflowed from the needle tips and maintained their extruded geometries asobservable by unmagnified inspection. Increasing the fumed silicacomposition to 15% resulted in more difficult needle extrusion butbetter fixity of extruded filament geometry. These silica-containinginks were then UV cured at 365 nm for 2 h and post-cured at 120° C. for24 h. When some loss of printed geometry was observed after post-curing,DMPA photoinitiator composition was increased to 5 wt % for the 15 wt %fumed silica sample, and the above process was repeated, after which thesyringe-printed geometries were fixed and maintained.

Porous Substrate Preparation:

SEM images (not shown here) revealed remaining rubber phases aftersolvent extraction of PS phases. These resulting polymers are bydefinition porous polymers with micro- or nanoporous morphologies.Consequently, the process for preparing micro- or nanoporous polymericsubstrates, and preparing such porous substrates through the processesdescribed herein, represent a route to recycling the recycled materialsproduced through the processes reported.

Example 4 One-Pot Thermal Aging Process

One pot Thermal Aging Process for Preparing Curable Formulations:

Twenty four formulations:

1. Dipentene dimercaptan-co-triallyl isocyanurate (denoted DPDM-co-TAIC)

2. Dipentene-dipercaptan-co-1,2,4-tivinylcyclohexane (denotedDPDM-co-TVC)

3. Dipentene dimercaptan-co-glyoxal bis(diallyl acetal) (denotedDPDM-co-GLTA)

4. Dipentene dimercaptan-co-glyoxal bis(diallyl acetal) (denotedDPDM-co-GLTA)

5. Dipentene dimercaptan-co-neopentyl glycol diacrylate (denotedDPDM-co-NPGDA)

6. Dipentene dimercaptan-co-tricyclodecane diacrylate (denotedDPDM-co-TCDDA)

7. Dipentene dimercaptan-co-polyethylene glycol diacrylate, M_(n)250/700(denoted DPDM-co-PEGDA-250/700)

8. Dipentene dimercaptan-co-trimethylolpropane triacrylate (denotedDPDM-co-TMPTA)

9. Dipentene dimercaptan-co-pentaerithritol tetracrylate (denotedDPDM-co-PETTA)

10. Dipentene dimercaptan-co-cyclohexanedimethanol diglycidyl ether(denoted DPDM-co-CHDMDGE)

11. Dipentene dimercaptan-co-neopentyl glycol diglycidyl ether (denotedDPDM-co-NPGDGE)

12. Dipentene dimercaptan-co-ethylene glycol diglycidyl ether (denotedDPDM-co-EGDGE)

13. Dipentene dimercaptan-co-bisphenol A diglycidyl ether (denotedDPDM-co-BADGE)

14. Dipentene dimercaptan-co-glycerol diglycidyl ether (denotedDPDM-co-GDGE)

15. Dipentene dimercaptan-co-1,4-butanediol diglycidyl ether (denotedDPDM-co-BDDGE)

16. Dipentene dimercaptan-co-hydrogenated bisphenol A diglycidyl ether(denoted DPDM-co-HBADGE)

17. Dipentene dimercaptan-co-sorbitol polyglycidyl ether (denotedDPDM-co-SPGE)

18. Dipentene dimercaptan-co-triphenylolmethane triglycidyl ether(denoted DPDM-co-TPMTGE)

19. Dipentene dimercaptan-co-N,N-diglycidyl-4-glycidyloxyaniline(denoted DPDM-co-NGA)

20. Dipentene dimercaptan-co-4,4′-Methylenebis(N,N-diglycidylaniline)(denoted DPDM-co-4MGA)

21. Dipentene dimercaptan-co-epoxidized butadiene oligomer (denotedDPDM-co-EBD)

22. Dipentene dimercaptan-co-epoxidized butadiene/nitrile oligomer(denoted DPDM-co-EBDN)

23. Dipentene dimercaptan-co-epoxidized polyamide oligomer (denotedDPDM-co-EPAM); and

24. Dipentene dimercaptan-co-resorcinol diglycidyl ether (denotedDPDM-co-RDGE) were prepared from a mercaptanized terpene, dipentenedimercaptan, and a variety of non-mercaptinized constituents havingvarying chemical functionalities using one-pot synthetic processes byadding the respective constituents to a sealable glass reaction jars (40mL up to 1 L in size) with thermosetting caps rated up to 150° C. Afterone-pot addition of the respective constituents to the sealable glassjars, additional modifier constituents (see above for definitions) wereoptionally added to tailor the physical and thermomechanical propertiesof the resulting materials 1-24 listed above in stoichiometricequivalents ranging from 0.01 to 5.00 to the above species 1-24.

The modifiers were added in concentrations ranging from 0.1 to 90 mole %to modify the physical and/or thermomechanical properties of the uncuredformulations and the cured formulations and mixtures thereof.

The formulations with or without added modifiers were subjected to athermal aging processes by heating the prepared formulations in sealedcontainers to temperatures ranging from about 0° C. to 80° C. for timesranging from 0.01 h to 24 h, optionally under a gentle vortex agitationusing a LabConco RapidVap instrument at a vortex speed of 15. Thermalaging is not essential to this method but can be beneficial.

During the thermal aging process, various addition reactions with nochemical by-products were selectively carried out in order to modify themolecular and macromolecular properties of the species being formedduring thermal aging for the purpose of tuning the physical, mechanical,and/or thermomechanical properties and curing profiles of the uncuredcurable formulations and the physical, mechanical, and/orthermomechanical properties of the curable formulations when cured.Chemical addition reactions carried out during the thermal agingprocesses included free radical-initiated thiol-ene addition by usingthermal initiators, such as AIBN in 0.01 to 10 wt % concentrations, basecatalyzed thiol-acrylate and amine-acrylate Michael Additions usingtertiary amine catalysts such as triethylene diamine in 0.001 to 10 wt %concentrations, base catalyzed thiol-epoxy and thiol-amine reactionsusing tertiary amine catalysts such as triethylene diamine in 0.001 to10 wt % concentrations.

After thermal aging, the formulations were either stored for futurecuring or blended with other formulations and additional modifiers andthen stored for curing. Viscosities of thermally aged formulations didnot increase after 60 days of storage at 25° C. It was noted that allthermally aged formulations except for those containing free acrylatespecies exhibited no increase in viscosity after heating to 80° C. for72 h.

Characterization of Uncured and Cured Formulations:

Approximate viscosities for thermally aged formulations were measuredusing the Zahn cup method (ASTM D4212). Thermomechanical assessments ofeach formulation material were carried out using a qualitative materialinspection assessment. Characterization data and notes about eachrespective uncured and cured formulation are provided in Table 4 below.

TABLE 4 Cured Formulation Material Performance Summary FormulationModulus at (Cured) 20° C. Observations DPDM-co-TAIC Glassy Excellenttoughness & shape memory behavior, excellent water & solvent resistanceDPDM-co-TVC Viscoelastic to High energy damping, high Elastomericrecoverable viscoelastic deformation, good water & solvent resistanceDPDM-co-GLTA Viscoelastic to Poor mechanical integrity ElastomericDPDM-co-NPGDA Glassy to Good toughness in viscoelastic Viscoelasticregime near 25° C. DPDM-co-TCDDA Glassy Good toughness in glassy regimenear 25° C. DPDM-co- Viscoelastic to Good toughness in viscoelasticPEGDA-250/700 Glassy regime near 25° C. DPDM-co-TMPTA Glassy Averagetoughness in glassy regime near 25° C. DPDM-co-PETTA Glassy Goodtoughness in glassy regime near 25° C. DPDM-co- Glassy Good toughnessnear 25° C., CHDMDGE good sunlight resistance DPDM-co- Viscoelastic toGood flexibility near 25° C. NPGDGE Elastomeric DPDM-co-EGDGEViscoelastic to Good flexibility near 25° C. Elastomeric DPDM-co-BADGEGlassy Good flexibility near 25° C. DPDM-co-GDGE Viscoelastic Goodflexibility near 25° C. DPDM-co-BDDGE Viscoelastic Good flexibility near25° C. DPDM-co- Glassy Good toughness near 25° C., HBADGE good sunlightresistance DPDM-co-SPGE Glassy Good toughness near 25° C. DPDM-co-Glassy High rigidity TPMTGE DPDM-co-NGA Glassy Good toughness in glassstate near 25° C. DPDM-co-4MGA Glassy High rigidity DPDM-co-EBDElastomeric High flexibility near 25° C., good strain capacityDPDM-co-EBDN Elastomeric High flexibility near 25° C., good straincapacity DPDM-co-EPAM Glassy Good toughness in glass state near 25° C.DPDM-co-RDGE Glassy Good toughness in glass state near 25° C. “Goodtoughness” is defined as an approximate toughness of 2.50 MJ/m³ to 4.99MJ/m³. “Excellent toughness” is defined as an approximate toughness of5.0 J/m³ to 50.00 MJ/m³. “High” rigidity refers to an approximatestorage modulus of 900 MPa at 1 Hz and 25° C. “High recoverableviscolelastic deformation refers to an approximate recoverabledeformation of 20% to 500%.

Film Substrate Preparation:

To prepare UV curable film samples, liquid formulations were injected bypipet into 2.0″×3.0″×1.0 mm glass molds and then subjected to 365 nm or410 nm UV irradiation at energy doses ranging from 0.001 J/cm² to 60J/cm². After UV curing, films for each formulation were cut into twoseparate 1.5″×1.0″×1.0 mm films, of which one film of each formulationwas stored without post-curing and the other film of each formulationwas post-cured at 200° C. for 5 min. To prepare thermally curable orbase curable film samples, reactive thermally curable systems were mixedin desired ratios, and then 5 g of each formulation or mixture waspoured into a polypropylene mold and cured using temperatures rangingfrom 20° C. to 120° C. for times ranging from 10 seconds to 14 days.

Fumed Silica Addition:

Fumed silica nanoparticles were added to selected curable formulations,including DPDM-co-TAIC. A 20 g scale of 3 wt % mixture of fumed silicananoparticles with an average particle size of 200 m² and an uncuredDPDM-co-TAIC formulation with 2 wt % DMPA photoinitiator was heated to80 C for 1 h in a 40 mL glass vial and shaken twice by hand duringheating. After 1 h, fumed silica dispersion appeared to be homogeneous,and the silica/uncured formulation mixture was translucent with aviscosity at 25 C that appeared suitable for low-viscosity manufacturingprocesses including DLP and SLA 3D printing. Fumed silica was added bothto modify rheology of uncured formulations and to tailor mechanicalstrength of cured materials. Specifically, fumed silica was added toincrease the toughness of cured materials at temperatures significantlyabove glass transition but below thermal decomposition.

UV Curable Formulations & Mixtures Processed by Photojet &Stereolithography Additive (SLA) Manufacturing:

The UV curable formulations above were subjected to photojet andstereolithography additive (SLA) manufacturing techniques. Exemplaryformulations of resins subjected to photojet 3-D printing includedipentene dimercaptan (DPDM)-co-triallyl isocyanurate (DPDM-co-TAIC),using a 1.0:1.0 SH:C═C stoichiometric ratio, 2.0 wt % DMPAphotoinitiator (2,2-dimethoxy-2-phenylacetophenone), and up to 500 ppm4-methoxyphenol free radical inhibitor. This cured formulation exhibiteda viscosity of 6-7 cP at 50° C. and was consequently jettable. Anotherjettable formulation was formed of D-limonene-co-[0.50 TMPTMP:0.501,10-decanedithiol], 1.0:1.0 C═C: SH stoichiometric ratio, 5.0 wt % DMPAphotoinitiator. This cured formulation exhibited a viscosity of ˜20 cPat 50° C. and was also jettable. Photojet additive manufacturing wascarried out using a proprietary inkjet 3D printer that uses 365 nm UVirradiation to harden low viscosity photocurable resins immediatelyafter jetting. A printed scaffold structure with approximately a 200micron scaffold strut feature resolution (not shown) formed of the aboveD-limonene-co-[0.50 TMPTMP : 0.50 1,10-decanedithiol] was achieved.

For processing by SLA additive manufacturing, formulations were printedusing a FORMLABS@ Form2 commercially available 3-D printer. An exemplaryformulation for SLA 3-D printing is dipentenedimercaptan-co-trimethylolpropane triacrylate (DPDM-co-TMPTA), using a1.0:2.0 acrylate:SH stoichiometric ratio, 0.40 wt % TPO photoinitiator(2,4,6-Trimethylbenzoyl-0.16 wt % OB+UV blocker(2,2′-(2,5-thiophenediyl)bis(5-tert-butylbenzoxazole)), and up to 500ppm 4-methoxyphenol free radical inhibitor. To demonstrate that thisformulation could be successfully 3-D printed using the Formlabs Form2SLA printer, a standard support base was printed using a 0.1 mm layerthickness, a density of 1.00, a point size of 0.60 mm, a flat spacing of5.00 mm, a slope multiplier of 1.00 and a base thickness of 2.00 mm.After printing, the 3D printed base was washed in isopropanol for 5 minand then post-cured using a DYMAX®˜405 nm UV cure chamber for 2 min. Thepost-cured 3D printed part was again washed in isopropanol for anadditional 60 sec and patted dry using a paper towel. This 2 mm-thickwashed and post-cured 3D printed base exhibited high rigidity, goodoptical clarity, excellent mechanical integrity, minimal yellowing andgood resistance to many solvents.

Stable Low-Viscosity Formulations for Manufacturing Techniques thatutilize 3-D Inkjet Processing:

Processing of one-part curable formulations with viscosities suitablefor ink jet processing (e.g., viscosity between 1.0 and 100.0 cP at 20°C.) were carried out successfully using a proprietary ink jet 3Dprinting system. The formulations being printed showed no increase inviscosity over a 4 week period and were compatible with the inkjetprocessing system's internal design materials and components thereof.Exemplary thiol-epoxy formulations are listed in Table 5 below, whereDPDM=dipentene dimercaptan, PETMP=pentaerithritoltetrakis(3-mercaptopropionate), TMPTMP=trimethylolpropanetris(3-mercaptopropionate), NPGDGE=neopentyl glycol diglycidyl ether,TMPTGE=trimethylolpropane triglycidyl ether,CHDMDGE=cyclohexanedimethanol diglycidyl ether, and 2EHGE=2-ethylhexylglycidyl ether. Predicted viscosities were calculated using a parallelmixing equation in which viscosity for formulations was calculated to bethe sum of the products of the volume fraction of each constituentmultiplied by the viscosity of each constituent.

TABLE 5 Exemplary formulations, calculated viscosities, epoxy/SH ratios,and average epoxy and SH functionalities (F_(av)) for jettablelow-viscosity resins used in inkjet processing techniques Calcu- latedViscos- ity Epoxy/ F_(av) F_(av) Formulation (cP) SH Epoxy SH 1. [0.90DPDM:0.10 PETMP]-co- 43.1 0.934 2.22 2.16 [0.40 NPGDGE:0.60 TMPTGE:0.152EHGE] 2. [0.80 DPDM:0.20 TMPTMP-co- 37.4 0.934 2.20 2.18 [0.50NPGDGE:0.45 TMPTGE:0.10 2EHGE] 3. [0.90 DPDM:0.10 PETMP]-co- 34.3 1.0352.06 2.16 [0.75 NPGDGE:0.20 TMPTGE:0.10 2EHGE] 4. [0.75 DPDM:0.25TMPTMP-co- 36.5 1.050 2.11 1.91 [0.40 NPGDGE:0.20 TMPTGE:0.25CHDMDGE:0.20 2EHGE] 5. DPDM-co-[0.70 NPGDGE:0.30 23.6 1.000 2.31 1.91TMPTGE] 6. [0.725 DPDM:0.275 TMPTMP]- 42.00 1.148 2.24 2.27 co-[0.35NPGDGE:0.5 TMPTGE:0.15 CHDMDGE]

The formulated thiol-epoxy mixtures, such as those listed in Table 5above, were mixed in total mixture quantities ranging from 5 mL to 20 L.To demonstrate the stability of each formulation, each formulatedmixture was heated to 80° C. for 24 hours and was shown to maintain aconstant viscosity before and after heating. The formulations weresubjected to inkjet processing techniques used in various manufacturingprocesses. In one exemplary process, sebacic acid nano- and micropowderswere impregnated by mixing with a small amount of tertiary aminecatalysts (approximately 0.1 to 10.0 wt %) that included triethylenediamine (TEDA=“DABCO”) using a FlackTek® DAC 150 speed mixer. Aminecatalyst-impregnated sebacic acid powders were poured into and spreadevenly throughout 8″×12″×2″ glass pans, and formulated thiol-epoxymixtures were jetted onto the powder surfaces from 25, 50, 100, 150 and250 μm nozzles in a controlled manner representative of that of aprinthead used in inkjet printing processes to form pre-designed shapes.As liquid thiol-epoxy formulated resins were jetted onto powdersurfaces, excellent wetting to sebacic acid and other powders (e.g.,sand, polymer powders, hydroxyapatite nanopowder, tungsten powder, etc.)was observed, and jetted thiol-epoxy resins hardened to form powder-richcomposite materials within minutes to hours to days after jetting ontopowders

Coatings:

Uncured formulations (neat, or dissolved or dispersed in a solvent orwater) were applied as coatings between 1 micron to 300 microns inthickness using roll coating, spray coating, brush coating and hot meltcoating techniques. For solvent/water dissolved/dispersed coatings,drying time was tunable between 5 min and 5 days. For 100% solids UVcurable coatings, full cure occurred with irradiation energies rangingfrom 0.15 mJ/cm² to 5.0 J/cm².

A dipentene dimercaptan (DPDM)-co-triallyl isocyanurate coating with 3.0wt % EVONIK® Aerosil R972 fumed silica (varying photoinitiator, 0.1 to5.0 wt %, DMPA and TPO photonitiator) was prepared by mixing DPDM/TAICand fumed silica in a FlackTek® speed mixer at a 3000 RPM for 90seconds. The resulting mixture's viscosity remained very low,approximately 20-60 cP at 25 C. This mixture was applied to a glasssubstrate using a BYRD bar at a 2 mil thickness and cured using UVirradiation with irradiation doses varying from 0.10 mJ/cm² to 5.0 J/cm²(wavelengths=365 nm and 390-410 nm). This DPDM-co-TAIC+3.0 wt % AerosilR972 UV cured formulation passed a proprietary glass adhesion testadministered within the printing industry.

Those skilled in the art will recognize, or be able to ascertain usingno more than routine experimentation, many equivalents to the specificembodiments of the invention described herein. Such equivalents areintended to be encompassed by the following claims.

We claim:
 1. A curable formulation, the formulation comprising: apolythiol constituent; an alkene-containing and/or alkyne-containingconstituent; and an epoxy-containing constituent.
 2. The curableformulation of claim 1, wherein the polythiol constituent is derivedfrom a mercaptan-containing terpene or terpenoid, a mercaptan-containingcyclic alkene, a mercaptan-containing polycyclic alkene, a linearalkene, a mercaptan-containing alkyne, a mercaptan-containingunsaturated fatty acid, a mercaptan-containing unsaturated fatty ester,or a mercaptan-containing polyalkene.
 3. The curable formulation ofclaim 1, wherein the polythiol constituent is derived fromtrimethylolpropane trithiol, pentaerithritiol trithiol, pentaerithritoltetrathiol, inositol, and dithiols, trithiols, tetrathiols, pentathiols,hexathiols, or combinations thereof.
 4. The curable formulation of claim2, comprising a mercaptan-containing terpene or terpenoid selected fromthe group consisting of dipentene dimercaptan, isoprene dimercaptan,farnesene dimercaptan, farnesene trimercaptan, farnesene tetramercaptan,myrcene dimercaptan, myrcene trimercaptan, bisabolene dimercaptan,bisabolene trimercaptan, linalool dimercaptan, terpinolene dimercaptan,terpinene dimercaptan, geraniol dimercapan, citral dimercaptan, retinoldimercaptan, retinol trimercaptan, retinol tetramercaptan, beta-carotenepolymercaptans, and combinations thereof.
 5. The curable formulation ofclaim 2, comprising a mercaptan-containing cyclic alkene,mercaptan-containing polycyclic alkene, or linear aliphatic alkeneselected from the group consisting of trivinylcyclohexene dimercaptan,trivinylcyclohexene trimercaptan, dicyclopentadiene dimercaptan,vinylcyclohexene dimercaptan, triallylisocyanurate dimercaptan, triallylisocyanurate trimercaptan, and combinations thereof.
 6. The curableformulation of claim 2, wherein the mercaptan-containing alkyne isselected from the group consisting of phenylhepta-1,3,5-triynepolymercaptans, 2-butyne-1,4-diol dimercaptan, propargyl alcoholdimercaptan, dipropargyl sulfide polymercaptans, dipropargyl etherpolymercaptans, propargylamine dimercaptan, dipropargylaminepolymercaptans, tripropargylamine polymercaptans, tripropargylisocyanurate polymercaptans, tripropargyl cyanurate polymercaptans, andcombinations thereof.
 7. The curable formulation of claim 2, comprisingmercaptan-containing fatty acids or fatty acid esters selected from thegroup consisting of arachidonic acid dimercaptan, arachidonic acidtrimercaptan, arachidonic acid tetramercaptan, eleostearic aciddimercaptan, eleostearic acid trimercaptan, linoleic acid dimercaptan,linolenic acid dimercaptan, linolenic acid trimercaptan, mercaptanizedlinseed oil, mercaptanized tung oil, mercaptanized soybean oil,mercaptanized peanut oil, mercaptanized walnut oil, mercaptanizedavocado oil, mercaptanized sunflower oil, mercaptanized corn oil,mercaptanized cottonseed oil, and combinations thereof.
 8. The curableformulation of claim 2, comprising a alkene constituent selected fromthe group consisting of terpenes, terpenoids, dimerized terpene,dimerized terpenoids, trimerized terpenes, trimerized terpenoids,oligomeric terpenes or terpenoids, polymerized terpenes, polymerizedterpenoids, limonene, D-limonene, L-limonene, poly(limonene), farnesene,myrcene, bisabolene, linalool, terpinolene, terpinene, geraniol, citral,retinol, beta-carotene, triallyl isocyanurate, 1,2,4-trivinylcyclohexane, norbornene functionalized poly(terpene) oligomers,norbomene-functionalized polydimethylsiloxane, norbomene-functionalizedpoly(butadiene), norbomene-functionalized polyisoprene oligomers,poly(isoprene), divinyl ether, triallylamine, diallylamine, diallylbisphenol A, cyclohexanedimethanol diallyl ether, pentaerithritoltetraallyl ether, trimethylolpropane triallyl ether,2,4,6-triallyloxy-1,3,5-triazine, inositol diallyl ether, inositoltriallyl ether, inositol tetraallyl ether, inositol pentaallyl ether,inositol hexaallyl ether, inositol divinyl ether, inositol trivinylether, inositol tetravinyl ether, inositol pentavinyl ether, inositolhexavinyl ether, triallyl citrate, trivinyl citrate, 1,5-cyclooctadiene,1,3-cyclooxtadiene, 1,4-cyclooctadiene, 1,3-6 cyclooctatriene,cyclohexane diallyl ether, cyclohexane triallyl ether, cyclohexanetetraallyl ether, cyclohexane pentaallyl ether, cyclohexane hexaallylether, cyclohexane divinyl ether, cyclohexane trivinyl ether,cyclohexane tetravinyl ether, cyclohexane pentavinyl ether, cyclohexanehexavinyl ether, diclyclopentadiene, tricyclodecane dimethanol divinylether, tricyclodecane dimethanol diallyl ether, tricyclodecanedimethanol, norbornene capped, bicyclo[2.2.1]hepta-2,5-diene,norbornene-functionlized polyamide oligomers, allyl ether-functionlizedpolyamide oligomers, vinyl ether-functionalized polyamide oligomers,norbornene-functionlized polydimethylsiloxane, allyl ether-functionlizedpolydimethylsiloxane, vinyl ether-functionlized polydimethylsiloxane,resorcinol diallyl ether, resorcinol divinyl ether, diallylamine,triallylamine, allylamine, and combinations thereof.
 9. The curableformulation of claim 1, comprising an acrylate or methacrylate group asthe alkylene group.
 10. The curable formulation of claim 9, wherein theacrylate or methacrylate group is selected from the group consisting ofneopentyl glycol diacrylate, glycerol diacrylate, glycerol triacrylate,ethylene glycol diacrylate, tetraethylene glycol diacrylate,trimethylolpropane triacrylate, tris[2-(acryloyloxy)ethyl] isocyanurate,pentaerithritol tetraacrylate, pentaerithritol triacrylate, ethoxylatedtrimethylolpropane triacrylate, ethyoxylated pentaerithritoltriacrylate, ethoxylated pentaerithritol tetraacrylate,poly(dimethylsiloxane) diacrylate, poly(isoprene) diacrylate,poly(butadiene-co-nitrile) diacrylate, polyethyleneglycol diacrylate,tricyclodecantedimethanol diacrylate, bisphenol A diacrylate,ethoxylated bisphenol A diacrylate, and methacrylated equivalentsthereof.
 11. The curable formulation of claim 1, comprising an alkyneconstituent selected from the group consisting of acetylene, propargylalcohol, 2-butyne-1,4-diol, phenylhepta-1,3,5-triyne, dipropargylsulfide, dipropargyl ether, propargylamine, dipropargylamine,tripropargylamine, tripropargyl isocyanurate, tripropargyl cyanurate,propargyl inositol, dipropargyl inositol, tripropargyl inositol,tetrapropargyl inositol, pentapropargyl inositol, hexapropargylinositol, dipropargylpiperazine, dipropargyl citrate, tripropargylcitrate, cyclohexanedimethanol propargyl ether, cyclohexanedimethanoldipropargyl ether, quinic acid lactone propargyl ether, quinic acidlactone dipropargyl ether, quinic acid lactone tripropargyl ether,tricyclodecanedimethanol propargyl ether, tricyclodecanedimethanoldipropargyl ether, bisphenol A bis(propargyl ether), hydrogenatedbisphenol A bis(propargyl ether), cyclohexane dipropargyl ether,cyclohexane tripropargyl ether, cyclohexane tetrapropargyl ether,cyclohexane pentapropargyl ether, cyclohexane hexapropargyl ether,propargyl resorcinol, dipropargyl resorcinol, and combinations thereof.12. The curable formulation of claim 1, comprising an epoxy-containingconstituent selected from the group consisting of epoxidized terpenes,epoxidized terpenoids, epoxidized dimerized terpenes, epoxidizeddimerized terpenoids, epoxidized trimerized terpenes, epoxidizedtrimerized terpenoids, epoxidized oligomeric terpenes, epoxidizedoligomeric terpenoids, epoxidized polymerized terpenes, epoxidizedpolymerized terpenoids, limonene oxide, limonene dioxide, poly(limoneneoxide), poly(isoprene oxide)-co-polyisoprene copolymers, poly(butadieneoxide)-co-polybutadiene copolymers, epoxidized farnesene, epoxidizedfarnesene, epoxidized myrcene, epoxidized bisabolene, epoxidizedlinalool, epoxidized terpinolene, epoxidized terpinene, epoxidizedgeraniol, epoxidized citral, epoxidized retinol, epoxidizedbeta-carotene, epoxidized arachidonic acid, epoxidized eleostearic acidepoxidized linoleic acid, epoxidized linolenic acid, epoxidized linseedoil, epoxidized tung oil, epoxidized soybean oil, epoxidized peanut oil,epoxidized walnut oil, epoxidized avocado oil, epoxidized sunflower oil,epoxidized corn oil, epoxidized cottonseed oil, epoxidized palm oil,epoxidized glycerol, glycerol diglycidyl ether, glycerol triglycidylether, epoxidized sorbitol, sorbitol diglycidyl ether, sorbitoltriglycidyl ether, sorbitol tetraglycidyl ether, sorbitol pentaglycidylether and sorbitol hexaglycidyl ether, cyclohexanedimethanol diglycidylether, resorcinol diglycidyl ether, bisphenol A diglycidyl ether,hydrogenated bisphenol A diglycidyl ether, neopentyl glycol diglycidylether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidylether, tetraethylene glycol diglycidyl ether, polydimethylsiloxanediglycidyl ether, epoxidized butadiene oligomers, epoxidizedbutadiene-co-polynitrile oligomers, epoxidized grapefruit mercaptan,ethoxylated bisphenol A diglycidyl ether, ethoxylated hydrogenatedbisphenol A diglycidyl ether, ethoxylated cyclohexanedimethanoldiglycidyl ether, and combinations thereof.
 13. The curable formulationof claim 2, further comprising one or more modifiers selected from thegroup consisting of trimethylolpropane tris(3-mercaptopropionate),pentaerithritol tetrakis(3-mercaptopropionate), dipentaerithritolhexakis(3-mercaptopropionate),tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, tetraethylene glycolbis(3-mercaptopropionate), 1,10-decanedithiol, ethylene glycolbis(3-mercaptopropionate), 1,2-ethanedithiol, 1,3-propanedithiol,1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol,2-mercaptoethanol, 2-hydroxyethylacrylate, 2-carboxyethylacrylate,acrylic acid, thioglycolic acid, iso-tridecyl 3-mercaptopropionate,sodium thioglycolate, butyl glycidyl ether, 2-ethylhexyl glycidyl ether,limonene oxide, limonene dioxide, dicyclopentadiene dioxide, castor oilglycidyl ether, 2-amino-2-methyl-1-propanol, vinyl cyclohexene oxide,allyl isothiocyanate, isophorone diisocyanate, bisphenol A ethoxylatediacrylate, bisphenol A ethoxylate diglycidyl ether, ethoxylatedtrimethylolpropane tris(3-mercaptopropionate), pentaerithritoltetrakis(polycaprolactone, mercaptopropionate terminated),polydimethylsiloxane, diglycidyl ether terminated, glycerol diacrylate,glycerol triacrylate, allyl glycidyl ether, and combinations thereof.14. The curable formulation of claim 1, further comprising one or moremodifiers selected from the group consisting of sand, polymer powders,hydroxyapatite nanopowder, tungsten powder, metal powders, ceramicpowders, and combinations thereof.
 15. A cured formulation, theformulation comprising one or more reaction products of: a polythiolconstituent; an alkene-containing and/or alkyne-containing constituent;and an epoxy-containing constituent.
 16. The cured formulation of claim15, wherein the polythiol constituent is derived from amercaptan-containing terpene or terpenoid, a mercaptan-containing cyclicalkene, a mercaptan-containing polycyclic alkene, a linear alkene, amercaptan-containing alkyne, a mercaptan-containing unsaturated fattyacid, a mercaptan-containing unsaturated fatty ester, or amercaptan-containing polyalkene.
 17. The cured formulation of claim 15,wherein the polythiol constituent is derived from trimethylolpropanetrithiol, pentaerithritiol trithiol, pentaerithritol tetrathiol,inositol, and dithiols, trithiols, tetrathiols, pentathiols, hexathiols,or combinations thereof.
 18. The cured formulation of claim 16, whereinthe mercaptan-containing terpene or terpenoid is selected from the groupconsisting of dipentene dimercaptan, isoprene dimercaptan, farnesenedimercaptan, farnesene trimercaptan, farnesene tetramercaptan, myrcenedimercaptan, myrcene trimercaptan, bisabolene dimercaptan, bisabolenetrimercaptan, linalool dimercaptan, terpinolene dimercaptan, terpinenedimercaptan, geraniol dimercapan, citral dimercaptan, retinoldimercaptan, retinol trimercaptan, retinol tetramercaptan, beta-carotenepolymercaptans, and combinations thereof.
 19. The cured formulation ofclaim 16, wherein the mercaptan-containing cyclic alkene,mercaptan-containing polycyclic alkene, or linear aliphatic alkene isselected from the group consisting of trivinylcyclohexene dimercaptan,trivinylcyclohexene trimercaptan, dicyclopentadiene dimercaptan,vinylcyclohexene dimercaptan, triallylisocyanurate dimercaptan, triallylisocyanurate trimercaptan, and combinations thereof.
 20. The curedformulation of claim 16, wherein the mercaptan-containing alkyne isselected from the group consisting of phenylhepta-1,3,5-triynepolymercaptans, 2-butyne-1,4-diol dimercaptan, propargyl alcoholdimercaptan, dipropargyl sulfide polymercaptans, dipropargyl etherpolymercaptans, propargylamine dimercaptan, dipropargylaminepolymercaptans, tripropargylamine polymercaptans, tripropargylisocyanurate polymercaptans, tripropargyl cyanurate polymercaptans, andcombinations thereof.
 21. The cured formulation of claim 16, wherein themercaptan-containing fatty acids or fatty acid esters are selected fromthe group consisting of arachidonic acid dimercaptan, arachidonic acidtrimercaptan, arachidonic acid tetramercaptan, eleostearic aciddimercaptan, eleostearic acid trimercaptan, linoleic acid dimercaptan,linolenic acid dimercaptan, linolenic acid trimercaptan, mercaptanizedlinseed oil, mercaptanized tung oil, mercaptanized soybean oil,mercaptanized peanut oil, mercaptanized walnut oil, mercaptanizedavocado oil, mercaptanized sunflower oil, mercaptanized corn oil,mercaptanized cottonseed oil, and combinations thereof.
 22. The curedformulation of claim 16, wherein the alkene constituent is selected fromthe group consisting of terpenes, terpenoids, dimerized terpene,dimerized terpenoids, trimerized terpenes, trimerized terpenoids,oligomeric terpenes or terpenoids, polymerized terpenes, polymerizedterpenoids, limonene, D-limonene, L-limonene, poly(limonene), farnesene,myrcene, bisabolene, linalool, terpinolene, terpinene, geraniol, citral,retinol, beta-carotene, triallyl isocyanurate, 1,2,4-trivinylcyclohexane, norbornene functionalized poly(terpene) oligomers,norbomene-functionalized polydimethylsiloxane, norbomene-functionalizedpoly(butadiene), norbomene-functionalized polyisoprene oligomers,poly(isoprene), divinyl ether, triallylamine, diallylamine, diallylbisphenol A, cyclohexanedimethanol diallyl ether, pentaerithritoltetraallyl ether, trimethylolpropane triallyl ether,2,4,6-triallyloxy-1,3,5-triazine, inositol diallyl ether, inositoltriallyl ether, inositol tetraallyl ether, inositol pentaallyl ether,inositol hexaallyl ether, inositol divinyl ether, inositol trivinylether, inositol tetravinyl ether, inositol pentavinyl ether, inositolhexavinyl ether, triallyl citrate, trivinyl citrate, 1,5-cyclooctadiene,1,3-cyclooxtadiene, 1,4-cyclooctadiene, 1,3-6 cyclooctatriene,cyclohexane diallyl ether, cyclohexane triallyl ether, cyclohexanetetraallyl ether, cyclohexane pentaallyl ether, cyclohexane hexaallylether, cyclohexane divinyl ether, cyclohexane trivinyl ether,cyclohexane tetravinyl ether, cyclohexane pentavinyl ether, cyclohexanehexavinyl ether, diclyclopentadiene, tricyclodecane dimethanol divinylether, tricyclodecane dimethanol diallyl ether, tricyclodecanedimethanol, norbomene capped, bicyclo[2.2.1]hepta-2,5-diene,norbornene-functionlized polyamide oligomers, allyl ether-functionlizedpolyamide oligomers, vinyl ether-functionalized polyamide oligomers,norbornene-functionlized polydimethylsiloxane, allyl ether-functionlizedpolydimethylsiloxane, vinyl ether-functionlized polydimethylsiloxane,resorcinol diallyl ether, resorcinol divinyl ether, diallylamine,triallylamine, allylamine, and combinations thereof.
 23. The curedformulation of claim 15, wherein the alkene constituent is an acrylateor methacrylate group.
 24. The cured formulation of claim 23, whereinthe acrylate or methacrylate group is selected from the group consistingof neopentyl glycol diacrylate, glycerol diacrylate, glyceroltriacrylate, ethylene glycol diacrylate, tetraethylene glycoldiacrylate, trimethylolpropane triacrylate, tris[2-(acryloyloxy)ethyl]isocyanurate, pentaerithritol tetraacrylate, pentaerithritoltriacrylate, ethoxylated trimethylolpropane triacrylate, ethyoxylatedpentaerithritol triacrylate, ethoxylated pentaerithritol tetraacrylate,poly(dimethylsiloxane) diacrylate, poly(isoprene) diacrylate,poly(butadiene-co-nitrile) diacrylate, polyethyleneglycol diacrylate,tricyclodecantedimethanol diacrylate, bisphenol A diacrylate,ethoxylated bisphenol A diacrylate, and methacrylated equivalentsthereof.
 25. The cured formulation of claim 15, wherein the alkyneconstituent is selected from the group consisting of acetylene,propargyl alcohol, 2-butyne-1,4-diol, phenylhepta-1,3,5-triyne,dipropargyl sulfide, dipropargyl ether, propargylamine,dipropargylamine, tripropargylamine, tripropargyl isocyanurate,tripropargyl cyanurate, propargyl inositol, dipropargyl inositol,tripropargyl inositol, tetrapropargyl inositol, pentapropargyl inositol,hexapropargyl inositol, dipropargylpiperazine, dipropargyl citrate,tripropargyl citrate, cyclohexanedimethanol propargyl ether,cyclohexanedimethanol dipropargyl ether, quinic acid lactone propargylether, quinic acid lactone dipropargyl ether, quinic acid lactonetripropargyl ether, tricyclodecanedimethanol propargyl ether,tricyclodecanedimethanol dipropargyl ether, bisphenol A bis(propargylether), hydrogenated bisphenol A bis(propargyl ether), cyclohexanedipropargyl ether, cyclohexane tripropargyl ether, cyclohexanetetrapropargyl ether, cyclohexane pentapropargyl ether, cyclohexanehexapropargyl ether, propargyl resorcinol, dipropargyl resorcinol, andcombinations thereof.
 26. The cured formulation of claim 15, wherein theepoxy-containing constituent is selected from the group consisting ofepoxidized terpenes, epoxidized terpenoids, epoxidized dimerizedterpenes, epoxidized dimerized terpenoids, epoxidized trimerizedterpenes, epoxidized trimerized terpenoids, epoxidized oligomericterpenes, epoxidized oligomeric terpenoids, epoxidized polymerizedterpenes, epoxidized polymerized terpenoids, limonene oxide, limonenedioxide, poly(limonene oxide), poly(isoprene oxide)-co-polyisoprenecopolymers, poly(butadiene oxide)-co-polybutadiene copolymers,epoxidized farnesene, epoxidized farnesene, epoxidized myrcene,epoxidized bisabolene, epoxidized linalool, epoxidized terpinolene,epoxidized terpinene, epoxidized geraniol, epoxidized citral, epoxidizedretinol, epoxidized beta-carotene, epoxidized arachidonic acid,epoxidized eleostearic acid epoxidized linoleic acid, epoxidizedlinolenic acid, epoxidized linseed oil, epoxidized tung oil, epoxidizedsoybean oil, epoxidized peanut oil, epoxidized walnut oil, epoxidizedavocado oil, epoxidized sunflower oil, epoxidized corn oil, epoxidizedcottonseed oil, epoxidized palm oil, epoxidized glycerol, glyceroldiglycidyl ether, glycerol triglycidyl ether, epoxidized sorbitol,sorbitol diglycidyl ether, sorbitol triglycidyl ether, sorbitoltetraglycidyl ether, sorbitol pentaglycidyl ether and sorbitolhexaglycidyl ether, cyclohexanedimethanol diglycidyl ether, resorcinoldiglycidyl ether, bisphenol A diglycidyl ether, hydrogenated bisphenol Adiglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycoldiglycidyl ether, 1,4-butanediol diglycidyl ether, tetraethylene glycoldiglycidyl ether, polydimethylsiloxane diglycidyl ether, epoxidizedbutadiene oligomers, epoxidized butadiene-co-polynitrile oligomers,epoxidized grapefruit mercaptan, ethoxylated bisphenol A diglycidylether, ethoxylated hydrogenated bisphenol A diglycidyl ether,ethoxylated cyclohexanedimethanol diglycidyl ether, and combinationsthereof.
 27. The cured formulation of claim 16, further comprising oneor more modifiers selected from the group consisting oftrimethylolpropane tris(3-mercaptopropionate), pentaerithritoltetrakis(3-mercaptopropionate), dipentaerithritolhexakis(3-mercaptopropionate),tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, tetraethylene glycolbis(3-mercaptopropionate), 1,10-decanedithiol, ethylene glycolbis(3-mercaptopropionate), 1,2-ethanedithiol, 1,3-propanedithiol,1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol,2-mercaptoethanol, 2-hydroxyethylacrylate, 2-carboxyethylacrylate,acrylic acid, thioglycolic acid, iso-tridecyl 3-mercaptopropionate,sodium thioglycolate, butyl glycidyl ether, 2-ethylhexyl glycidyl ether,limonene oxide, limonene dioxide, dicyclopentadiene dioxide, castor oilglycidyl ether, 2-amino-2-methyl-1-propanol, vinyl cyclohexene oxide,allyl isothiocyanate, isophorone diisocyanate, bisphenol A ethoxylatediacrylate, bisphenol A ethoxylate diglycidyl ether, ethoxylatedtrimethylolpropane tris(3-mercaptopropionate), pentaerithritoltetrakis(polycaprolactone, mercaptopropionate terminated),polydimethylsiloxane, diglycidyl ether terminated, glycerol diacrylate,glycerol triacrylate, allyl glycidyl ether, and combinations thereof.28. The cured formulation of claim 15, further comprising one or moremodifiers selected from the group consisting of sand, polymer powders,hydroxyapatite nanopowder, tungsten powder, metal powders, ceramicpowders, and combinations thereof.
 29. The cured formulation of claim15, wherein the viscosity is stable at 25° C. for at least 30 days, atleast 60 days, or at least 90 days, when the formulation is stored underlight-free storage conditions.
 30. A method of making the curableformulation of claim 1 comprising the steps of: (a) mixing a polythiolconstituent; an alkene-containing and/or alkyne-containing constituent;and an epoxy-containing constituent; and (b) thermally aging themixture.
 31. The method of claim 30, wherein the polythiol constituentis derived from a mercaptan-containing terpene or terpenoid, amercaptan-containing cyclic alkene, a mercaptan-containing polycyclicalkene, a linear alkene, a mercaptan-containing alkyne, amercaptan-containing unsaturated fatty acid, a mercaptan-containingunsaturated fatty ester, or a mercaptan-containing polyalkene.
 32. Themethod of claim 30, wherein the polythiol constituent is derived fromtrimethylolpropane trithiol, pentaerithritiol trithiol, pentaerithritoltetrathiol, inositol, and dithiols, trithiols, tetrathiols, pentathiols,hexathiols, or combinations thereof.
 33. The method of claim 31, whereinthe mercaptan-containing terpene or terpenoid is selected from the groupconsisting of dipentene dimercaptan, isoprene dimercaptan, farnesenedimercaptan, farnesene trimercaptan, farnesene tetramercaptan, myrcenedimercaptan, myrcene trimercaptan, bisabolene dimercaptan, bisabolenetrimercaptan, linalool dimercaptan, terpinolene dimercaptan, terpinenedimercaptan, geraniol dimercapan, citral dimercaptan, retinoldimercaptan, retinol trimercaptan, retinol tetramercaptan, beta-carotenepolymercaptans, and combinations thereof.
 34. The method of claim 31,wherein the mercaptan-containing cyclic alkene, mercaptan-containingpolycyclic alkene, or linear aliphatic alkene is selected from the groupconsisting of trivinylcyclohexene dimercaptan, trivinylcyclohexenetrimercaptan, dicyclopentadiene dimercaptan, vinylcyclohexenedimercaptan, triallylisocyanurate dimercaptan, triallyl isocyanuratetrimercaptan, and combinations thereof.
 35. The method of claim 31,wherein the mercaptan-containing alkyne is selected from the groupconsisting of phenylhepta-1,3,5-triyne polymercaptans, 2-butyne-1,4-dioldimercaptan, propargyl alcohol dimercaptan, dipropargyl sulfidepolymercaptans, dipropargyl ether polymercaptans, propargylaminedimercaptan, dipropargylamine polymercaptans, tripropargylaminepolymercaptans, tripropargyl isocyanurate polymercaptans, tripropargylcyanurate polymercaptans, and combinations thereof.
 36. The method ofclaim 31, wherein the mercaptan-containing fatty acids or fatty acidesters is selected from the group consisting of arachidonic aciddimercaptan, arachidonic acid trimercaptan, arachidonic acidtetramercaptan, eleostearic acid dimercaptan, eleostearic acidtrimercaptan, linoleic acid dimercaptan, linolenic acid dimercaptan,linolenic acid trimercaptan, mercaptanized linseed oil, mercaptanizedtung oil, mercaptanized soybean oil, mercaptanized peanut oil,mercaptanized walnut oil, mercaptanized avocado oil, mercaptanizedsunflower oil, mercaptanized corn oil, mercaptanized cottonseed oil, andcombinations thereof.
 37. The method of claim 31, wherein the alkeneconstituent is selected from the group consisting of terpenes,terpenoids, dimerized terpene, dimerized terpenoids, trimerizedterpenes, trimerized terpenoids, oligomeric terpenes or terpenoids,polymerized terpenes, polymerized terpenoids, limonene, D-limonene,L-limonene, poly(limonene), farnesene, myrcene, bisabolene, linalool,terpinolene, terpinene, geraniol, citral, retinol, beta-carotene,triallyl isocyanurate, 1,2,4-trivinyl cyclohexane, norbornenefunctionalized poly(terpene) oligomers, norbornene-functionalizedpolydimethylsiloxane, norbornene-functionalized poly(butadiene),norbornene-functionalized polyisoprene oligomers, poly(isoprene),divinyl ether, triallylamine, diallylamine, diallyl bisphenol A,cyclohexanedimethanol diallyl ether, pentaerithritol tetraallyl ether,trimethylolpropane triallyl ether, 2,4,6-triallyloxy-1,3,5-triazine,inositol diallyl ether, inositol triallyl ether, inositol tetraallylether, inositol pentaallyl ether, inositol hexaallyl ether, inositoldivinyl ether, inositol trivinyl ether, inositol tetravinyl ether,inositol pentavinyl ether, inositol hexavinyl ether, triallyl citrate,trivinyl citrate, 1,5-cyclooctadiene, 1,3-cyclooxtadiene,1,4-cyclooctadiene, 1,3-6 cyclooctatriene, cyclohexane diallyl ether,cyclohexane triallyl ether, cyclohexane tetraallyl ether, cyclohexanepentaallyl ether, cyclohexane hexaallyl ether, cyclohexane divinylether, cyclohexane trivinyl ether, cyclohexane tetravinyl ether,cyclohexane pentavinyl ether, cyclohexane hexavinyl ether,diclyclopentadiene, tricyclodecane dimethanol divinyl ether,tricyclodecane dimethanol diallyl ether, tricyclodecane dimethanol,norbornene capped, bicyclo[2.2.1]hepta-2,5-diene,norbornene-functionlized polyamide oligomers, allyl ether-functionlizedpolyamide oligomers, vinyl ether-functionalized polyamide oligomers,norbornene-functionlized polydimethylsiloxane, allyl ether-functionlizedpolydimethylsiloxane, vinyl ether-functionlized polydimethylsiloxane,resorcinol diallyl ether, resorcinol divinyl ether, diallylamine,triallylamine, allylamine, and combinations thereof.
 38. The method ofclaim 30, wherein the alkene constituent is an acrylate or methacrylategroup.
 39. The method of claim 38, wherein the acrylate or methacrylategroup is selected from the group consisting of neopentyl glycoldiacrylate, glycerol diacrylate, glycerol triacrylate, ethylene glycoldiacrylate, tetraethylene glycol diacrylate, trimethylolpropanetriacrylate, tris[2-(acryloyloxy)ethyl] isocyanurate, pentaerithritoltetraacrylate, pentaerithritol triacrylate, ethoxylatedtrimethylolpropane triacrylate, ethyoxylated pentaerithritoltriacrylate, ethoxylated pentaerithritol tetraacrylate,poly(dimethylsiloxane) diacrylate, poly(isoprene) diacrylate,poly(butadiene-co-nitrile) diacrylate, polyethyleneglycol diacrylate,tricyclodecantedimethanol diacrylate, bisphenol A diacrylate,ethoxylated bisphenol A diacrylate, and methacrylated equivalentsthereof.
 40. The method of claim 30, wherein the alkyne constituentselected from the group consisting of acetylene, propargyl alcohol,2-butyne-1,4-diol, phenylhepta-1,3,5-triyne, dipropargyl sulfide,dipropargyl ether, propargylamine, dipropargylamine, tripropargylamine,tripropargyl isocyanurate, tripropargyl cyanurate, propargyl inositol,dipropargyl inositol, tripropargyl inositol, tetrapropargyl inositol,pentapropargyl inositol, hexapropargyl inositol, dipropargylpiperazine,dipropargyl citrate, tripropargyl citrate, cyclohexanedimethanolpropargyl ether, cyclohexanedimethanol dipropargyl ether, quinic acidlactone propargyl ether, quinic acid lactone dipropargyl ether, quinicacid lactone tripropargyl ether, tricyclodecanedimethanol propargylether, tricyclodecanedimethanol dipropargyl ether, bisphenol Abis(propargyl ether), hydrogenated bisphenol A bis(propargyl ether),cyclohexane dipropargyl ether, cyclohexane tripropargyl ether,cyclohexane tetrapropargyl ether, cyclohexane pentapropargyl ether,cyclohexane hexapropargyl ether, propargyl resorcinol, dipropargylresorcinol, and combinations thereof.
 41. The method of claim 30,wherein the epoxy-containing constituent is selected from the groupconsisting of epoxidized terpenes, epoxidized terpenoids, epoxidizeddimerized terpenes, epoxidized dimerized terpenoids, epoxidizedtrimerized terpenes, epoxidized trimerized terpenoids, epoxidizedoligomeric terpenes, epoxidized oligomeric terpenoids, epoxidizedpolymerized terpenes, epoxidized polymerized terpenoids, limonene oxide,limonene dioxide, poly(limonene oxide), poly(isopreneoxide)-co-polyisoprene copolymers, poly(butadieneoxide)-co-polybutadiene copolymers, epoxidized farnesene, epoxidizedfarnesene, epoxidized myrcene, epoxidized bisabolene, epoxidizedlinalool, epoxidized terpinolene, epoxidized terpinene, epoxidizedgeraniol, epoxidized citral, epoxidized retinol, epoxidizedbeta-carotene, epoxidized arachidonic acid, epoxidized eleostearic acidepoxidized linoleic acid, epoxidized linolenic acid, epoxidized linseedoil, epoxidized tung oil, epoxidized soybean oil, epoxidized peanut oil,epoxidized walnut oil, epoxidized avocado oil, epoxidized sunflower oil,epoxidized corn oil, epoxidized cottonseed oil, epoxidized palm oil,epoxidized glycerol, glycerol diglycidyl ether, glycerol triglycidylether, epoxidized sorbitol, sorbitol diglycidyl ether, sorbitoltriglycidyl ether, sorbitol tetraglycidyl ether, sorbitol pentaglycidylether and sorbitol hexaglycidyl ether, cyclohexanedimethanol diglycidylether, resorcinol diglycidyl ether, bisphenol A diglycidyl ether,hydrogenated bisphenol A diglycidyl ether, neopentyl glycol diglycidylether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidylether, tetraethylene glycol diglycidyl ether, polydimethylsiloxanediglycidyl ether, epoxidized butadiene oligomers, epoxidizedbutadiene-co-polynitrile oligomers, epoxidized grapefruit mercaptan,ethoxylated bisphenol A diglycidyl ether, ethoxylated hydrogenatedbisphenol A diglycidyl ether, ethoxylated cyclohexanedimethanoldiglycidyl ether, and combinations thereof.
 42. The method of claim 30,wherein the mixture of step (a) further comprises one or more modifierswhich selected from the group consisting of trimethylolpropanetris(3-mercaptopropionate), pentaerithritoltetrakis(3-mercaptopropionate), dipentaerithritolhexakis(3-mercaptopropionate),tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, tetraethylene glycolbis(3-mercaptopropionate), 1,10-decanedithiol, ethylene glycolbis(3-mercaptopropionate), 1,2-ethanedithiol, 1,3-propanedithiol,1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol,2-mercaptoethanol, 2-hydroxyethylacrylate, 2-carboxyethylacrylate,acrylic acid, thioglycolic acid, iso-tridecyl 3-mercaptopropionate,sodium thioglycolate, butyl glycidyl ether, 2-ethylhexyl glycidyl ether,limonene oxide, limonene dioxide, dicyclopentadiene dioxide, castor oilglycidyl ether, 2-amino-2-methyl-1-propanol, vinyl cyclohexene oxide,allyl isothiocyanate, isophorone diisocyanate, bisphenol A ethoxylatediacrylate, bisphenol A ethoxylate diglycidyl ether, ethoxylatedtrimethylolpropane tris(3-mercaptopropionate), pentaerithritoltetrakis(polycaprolactone, mercaptopropionate terminated),polydimethylsiloxane, diglycidyl ether terminated, glycerol diacrylate,glycerol triacrylate, allyl glycidyl ether, and combinations thereof.43. The method of claim 30, wherein the mixture of step (a) furthercomprises one or more modifiers selected from the group consisting ofsand, polymer powders, hydroxyapatite nanopowder, tungsten powder, metalpowders, ceramic powders, and combinations thereof.
 44. The method ofmaking of claim 30, wherein the thermal aging step comprises applyingheat to the mixture at a temperature range between about 0° C. to about150° C.
 45. The method of making of claim 30, wherein the thermal agingstep is applied for a period of time of between about 0.01 hours toabout 24 hours.
 46. The method of making of claim 30, wherein thethermal aging step comprises agitation of the mixture.
 47. A method ofmaking a cured formulation, the method comprising the steps of: (a)mixing a polythiol constituent; an alkene-containing and/oralkyne-containing constituent; and an epoxy-containing constituent; (b)thermally aging the mixture; (c) adding an initiator or catalyst to themixture of step (a); and (d) curing the mixture of step (c).
 48. Themethod of claim 47, the curing step occurs by exposure of the mixture tolight or heat which decomposes the initiator.
 49. The method of claim47, wherein the initiator is 2,2-dimethoxy-2-phenylacetophenone ordiphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.
 50. A method ofprinting a curable formulation, the method comprising the steps of: (a)printing a thermally aged curable formulation comprising a polythiolconstituent; an alkene-containing and/or alkyne-containing constituent;and an epoxy-containing constituent; and (b) curing the printedformulation wherein the curing step is performed simultaneously with theprinting of the thermally aged curable formulation of step (a).
 51. Themethod of printing of claim 50, wherein the thermally aged curableformulation further comprises an initiator.
 52. The method of printingof claim 51, wherein the initiator is 2,2-dimethoxy-2-phenylacetophenoneor diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.
 53. The method ofprinting of claim 51, wherein the curing step comprises exposure of thejetted formulation to light or heat which decomposes the initiator. 54.The method of printing of claim 51, wherein the printing is performed bya stereolithographic additive printing, dynamic light projectionprinting, an inkjet printing, a photojet printing, or a direct writeprocess.
 55. The method of printing of claim 50, wherein the printingstep comprises jetting the thermally aged curable formulation into oneor more powders selected from the group consisting of sand, polymerpowders, hydroxyapatite powders, and tungsten powders.
 56. A coating ona substrate, the coating comprising a cured formulation comprising oneor more reaction products of: a polythiol constituent; analkene-containing and/or alkyne-containing constituent; and anepoxy-containing constituent.
 57. The coating of claim 56, wherein thesubstrate is formed of wood, wire, glass, metals, metal alloys,ceramics, or combinations thereof.
 58. The coating of claim 56, whereinthe coating has a thickness of about 0.01 microns to 300 microns.